JP6643066B2 - Manufacturing method of toner - Google Patents

Description

  The present invention relates to a method for producing a toner for developing an electrostatic image used in electrophotography, electrostatic recording, and the like.

In recent years, with the increasing demand for energy saving during image formation, efforts have been made to lower the fixing temperature of toner. As one of them, it has been proposed to further lower the fixing temperature by using a polyester having a low softening temperature. However, since the softening temperature is low, the toners may fuse with each other in a stationary state such as during storage or transportation, and blocking may occur.
Therefore, as means for achieving both blocking resistance and low-temperature fixability, a technique using a crystalline resin having a sharp melt property in which the viscosity is greatly reduced when the melting point is exceeded is proposed (Patent Documents 1 to 3).
However, when a crystalline polyester, which is a crystalline resin, is used alone as a binder resin, it is a major problem that the charge of the toner gradually escapes after frictional charging due to the low electric resistance of the crystalline polyester. Met.
Therefore, a toner has been proposed in which the amount of crystalline polyester added is reduced and an amorphous resin that is easily compatible with the crystalline polyester is mixed and used (Patent Document 4).
However, the following problems can occur when a toner containing an amorphous resin together with a crystalline polyester as a binder resin and resins that are easily compatible with each other are combined.
During the production of the toner, the amorphous resin and the crystalline polyester remain compatible while undergoing a step of heating and melting the crystalline polyester to a melting point or higher, or a step of dissolving the crystalline polyester using an organic solvent. Present in toner. As a result, the plasticization of the amorphous resin (that is, the lowering of the glass transition temperature) is induced, so that the sharp melt property is good, but the chargeability and the heat-resistant storage stability are not sufficient, and may deteriorate. Was.
On the other hand, in the case of a toner using a mixture of an amorphous resin that is hardly compatible with the crystalline polyester, the following problems may occur because the resins are hardly compatible with each other.
During the production of the toner, after the step of heating and melting above the melting point of the crystalline polyester, or after the step of dissolving the crystalline polyester using an organic solvent, the amorphous resin and the crystalline polyester phase-separated, A matrix-domain structure corresponding to the compatibility of the resin is spontaneously formed. As a result, plasticization of the amorphous resin (that is, lowering of the glass transition temperature) is not induced, and the chargeability and the heat-resistant storage stability are improved, but the low-temperature fixability is insufficient due to the low compatibility. Was not.
Therefore, in a case where resins that are easily compatible with each other are combined, as a method of phase-separating the crystalline polyester and the amorphous resin that are compatible with each other, the toner is heat-treated at a temperature close to and below the melting point of the crystalline polyester. There has been proposed a method in which an annealing step for promoting crystallization is provided, and phase separation is induced by crystallization of crystalline polyester (Patent Document 5).
On the other hand, as a method of suppressing the compatibilization during the production of the toner, the crystalline polyester is dissolved in a solvent, recrystallized by cooling, and then the crystalline polyester is mechanically pulverized and dispersed in the solvent. Thereafter, a method has been proposed in which a toner component containing an amorphous resin is dissolved or dispersed in the solvent to obtain a toner through a granulation step (Patent Document 6).

JP-B-56-13943 JP-B-62-39428 JP-A-4-120554 JP 2003-50478 A JP 2006-65077 A JP 2012-63534 A

When an annealing step of performing a heat treatment at a temperature close to and below the melting point of the crystalline polyester is provided as in Patent Document 5, crystallization of the crystalline polyester is promoted, and phase separation from the amorphous resin is induced. Is done. However, it is necessary to perform the annealing step for a long time or under a high-temperature condition in order to sufficiently phase-separate the crystalline polyester which has been once compatibilized and dissolved in the amorphous resin by heat treatment.
In this case, the crystalline polyester domain grows at the same time as the formation of the phase separation structure accompanying crystallization, so the crystalline polyester domain, which is a low-resistance component, is easily exposed on the toner surface, and the chargeability is not sufficient. There were cases.
As described in Patent Document 6, in the case of a method for producing a toner in which a crystalline polyester is recrystallized and then mechanically pulverized, the crystalline polyester and the amorphous resin are sufficiently phase-separated. It is possible to achieve both preservation and preservation. However, it is difficult to control the domain diameter of the crystalline polyester, and coarse domains exceeding 0.5 μm are generated. Further, after the crystalline polyester is dispersed in the solvent, the droplets are granulated to a toner size, so that it is difficult to uniformly generate domains of the crystalline polyester in the toner. As a result, the crystalline polyester domain, which is a low-resistance component, was likely to be exposed on the toner surface, and the chargeability was sometimes insufficient.
That is, in the conventional manufacturing method, in a combination in which the crystalline resin and the amorphous resin are compatible with each other, the crystalline resin and the amorphous resin are sufficiently phase-separated in the toner, and the crystalline resin is It was difficult to uniformly disperse the fine domains. Therefore, it has been difficult to achieve both low-temperature fixability, storage stability, and chargeability at a high level.

As a result of intensive studies, the present inventors have found that in a combination in which a crystalline resin and an amorphous resin are compatible with each other, the crystalline resin and the amorphous resin are sufficiently phase-separated in the toner, and It has been found that the following two points are important for uniformly dispersing the resin in fine domains.
First, the crystalline resin and the amorphous resin are once made compatible in the toner or the resin composition constituting the toner, and the crystalline resin and the amorphous resin are uniformly mixed.
Second, to form a phase-separated structure between the crystalline resin and the amorphous resin by a mechanism different from the crystal growth of the crystalline resin by the conventional heat treatment.
Specifically, it has been found that it is important to include the following steps in the toner manufacturing process.
(1) By heating above the melting point of the crystalline resin or dissolving with an organic solvent, the crystalline resin and the amorphous resin are compatibilized in the toner or the resin composition constituting the toner. Compatibilizing step to obtain a product.
(2) After the compatibilizing step, a step of adding a good solvent for the amorphous resin and a poor solvent for the crystalline resin to the compatibilized product to precipitate the crystalline resin.
Through these steps, in the toner or the resin composition constituting the toner, the crystalline resin is sufficiently phase-separated from the amorphous resin and forms fine and uniformly dispersed domains.

By using the above method, the reason why the crystalline resin is sufficiently phase-separated from the amorphous resin in the toner or the resin composition constituting the toner, and forms fine and uniformly dispersed domains is clear. It is not, but we guess as follows.
The mechanism of the present invention is different from the conventional mechanism of phase separation accompanying crystal growth of a crystalline resin by heat treatment. In the present invention, the difference between the solubility of the amorphous resin and the solubility of the crystalline resin in an organic solvent is utilized instead of simultaneously inducing the phase separation and the crystal growth of the crystalline resin.
That is, by adding a good solvent for the amorphous resin and a poor solvent for the crystalline resin, only the crystalline resin compatible with the amorphous resin is precipitated to induce phase separation. As a result, it is considered that sufficient phase separation could be induced in the toner or in the resin composition constituting the toner before the domain of the crystalline resin grew large.
That is, the method for producing a toner according to the present invention includes the steps of: dispersing the crystalline resin uniformly in the toner or the resin composition constituting the toner; And a step of compatibilizing with a hydrophilic resin. Further, in order to form fine domains of the crystalline resin, the crystalline resin once compatibilized with the crystalline resin is sufficient before the domain of the crystalline resin grows significantly in the toner or the resin composition constituting the toner. And a solvent treatment step for inducing phase separation.

That is, the present invention is a method for producing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin,
A compatibilizing step of compatibilizing the crystalline resin and the amorphous resin to obtain a compatibilized product, and
Including a solvent treatment step of treating the compatibilized product with an organic solvent,
Organic solvent is a good solvent of the non-crystalline resin, and, Ri poor solvent der of the crystalline resin,
The solvent treatment step, in an aqueous medium, a method of manufacturing a toner, wherein the step der Rukoto for processing compatibilizing material in the organic solvent.

  According to the present invention, it is possible to provide a method for producing a toner having both good low-temperature fixability and storage stability and good chargeability.

The method for producing the toner of the present invention (hereinafter also referred to as the method of the present invention)
A method for producing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin,
A compatibilizing step of compatibilizing the crystalline resin and the amorphous resin to obtain a compatibilized product, and
Including a solvent treatment step of treating the compatibilized product with an organic solvent,
The organic solvent is a good solvent for the amorphous resin and a poor solvent for the crystalline resin.
First, the compatibilizing step and the solvent treatment step using a specific organic solvent in the method of the present invention will be described.

<Compatibility>
In the present invention, the compatibility between a crystalline resin and an amorphous resin, which is necessary for developing low-temperature fixability of the toner, will be described.
As described above, when a toner is manufactured using a mixture of a crystalline resin and an amorphous resin that is hardly compatible with the crystalline resin, the resins are hardly compatible with each other. A corresponding matrix-domain structure is spontaneously formed. As a result, plasticization of the amorphous resin was not induced, and the low-temperature fixability was not sufficient. On the other hand, the present invention relates to a method for producing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin, wherein the crystalline resin is mixed uniformly in a resin composition constituting the toner. Since the resin can quickly induce plasticization of the entire toner, a high level of low-temperature fixability is exhibited.

<Compatibilization process>
In the present invention, the compatibilizing step is a step of compatibilizing a crystalline resin with an amorphous resin compatible with the crystalline resin (hereinafter, also simply referred to as an amorphous resin) to obtain a compatibilized product.
As a specific example, a step of heating the crystalline resin and the amorphous resin above the melting point of the crystalline resin to obtain a compatibilized product by dissolving the crystalline resin and the amorphous resin, or
The crystalline resin and the amorphous resin are dissolved in an organic solvent capable of dissolving the crystalline resin and the amorphous resin, and the compatibilized product is obtained by dissolving the crystalline resin and the amorphous resin with each other. Process. When the crystalline resin and the amorphous resin are compatible with each other, the compatibilized product may be obtained by cooling or removing the organic solvent.
The heating temperature in the compatibilizing step may be at least the melting point of the crystalline resin, more preferably at least 5 ° C. higher than the melting point of the crystalline resin, and still more preferably at least 10 ° C. higher than the melting point of the crystalline resin. Temperature.
On the other hand, the upper limit of the heating temperature in the compatibilization step is determined in consideration of the influence on cost and the like, and is not particularly limited, but is preferably a temperature that is higher by about 140 ° C. than the melting point of the crystalline resin. .
In the compatibilizing step,
(1) heating the crystalline resin and the amorphous resin above the melting point of the crystalline resin to melt the crystalline resin, or
(2) By dissolving the crystalline resin and the amorphous resin in an organic solvent capable of dissolving the crystalline resin and the amorphous resin, the crystalline resin is compatible with the high-affinity amorphous resin that coexists. It is solubilized to form a compatibilized product, and is in a state of being uniformly mixed in the resin composition constituting the toner.
As a result, at the time of fixing the toner, the crystalline resin uniformly mixed in the resin composition constituting the toner can promptly induce the plasticization of the entire toner, thereby exhibiting a high level of low-temperature fixing property.

Here, the compatibility between the crystalline resin and the amorphous resin is considered as follows.
In the compatibilizing step, the compatibilized product obtained by compatibilizing the crystalline resin and the amorphous resin preferably satisfies the following (formula 1).
0.00 ≦ {Wt / (Wr × Z / 100)} ≦ 0.50 (Equation 1)
Wt: heat of fusion (J / g) derived from the crystalline resin at the time of the second temperature rise in the measurement of the compatibilized material using a differential scanning calorimeter (DSC)
Wr: heat of fusion (J / g) at the time of the second temperature rise in the measurement of the crystalline resin using a differential scanning calorimeter (DSC)
Z: Content ratio (% by mass) of the crystalline resin in the compatibilized product

The measuring method of the differential scanning calorimeter (DSC) is as follows.
0.01 to 0.02 g of “a compatibilized product (solid matter) obtained by compatibilizing a crystalline resin and an amorphous resin” or “crystalline resin” is precisely weighed in an aluminum pan, The temperature is raised from 0 ° C. to 200 ° C. at a rate of temperature increase of 10 ° C./min, and a DSC curve at the first temperature increase is obtained.
Subsequently, it is cooled from 200 ° C. to −100 ° C. at a temperature lowering rate of 10 ° C./min, and again heated from −100 ° C. to 200 ° C. at a temperature increasing rate of 10 ° C./min to obtain a DSC curve at the second temperature raising. .
In the DSC curve at the time of the second heating, the heat of fusion (J / g) is determined from the area surrounded by a straight line extending from the low-temperature base line to the high-temperature side and the melting endothermic peak.

In the compatibilized product obtained in the compatibilizing step, the crystalline resin and the amorphous resin are compatible. Therefore, the crystalline resin in the compatibilized material is not sufficiently crystallized compared to the state before compatibilization, and as a result, the heat of fusion determined from the melting endothermic peak derived from the crystalline resin ( J / g).
The product of the heat of fusion of the crystal (Wr) observed in the crystalline resin alone and the content (Z) of the crystalline resin in the compatibilized product, which is the denominator of the above (formula 1), It means the heat of fusion when the contained crystalline resin is crystallized in the same manner as the crystalline resin alone.
Therefore, the compatibilized product obtained in the compatibilizing step has a higher degree of compatibility between the crystalline resin and the amorphous resin, in other words, a higher compatibility between the crystalline resin and the amorphous resin. , Wt become smaller than (Wr × Z / 100).
When the above {Wt / (Wr × Z / 100)} exceeds 0.50, the degree of compatibilization between the crystalline resin and the amorphous resin in the compatibilization step tends to decrease, and the crystallinity in the obtained toner tends to decrease. The uniform dispersibility of the conductive resin tends to decrease. Further, since the compatibility between the crystalline resin and the amorphous resin is low, plasticization of the amorphous resin is not sufficiently induced, and the low-temperature fixability tends to be reduced.
Further, {Wt / (Wr × Z / 100)} is more preferably 0.00 or more and 0.40 or less, and further preferably 0.00 or more and 0.30 or less. The smaller the value is, the easier it is to be compatible, and the uniform dispersibility of the crystalline resin in the toner can be improved.

In some cases, the compatibilized material contains a releasing agent or the like added as necessary, and a melting endothermic peak of the releasing agent or the like may be observed. The melting endothermic peak of the release agent and the like and the melting endothermic peak derived from the crystalline resin are determined by using the above-described scanning calorimetry method, the release agent and the like are measured alone, and the obtained melting endothermic peak and the crystal are determined. What is necessary is just to compare with the melting endothermic peak derived from the conductive resin. The release agent or the like may be obtained by extracting the release agent or the like from the compatibilized material by Soxhlet extraction using a hexane solvent, or using a release agent actually added.
Through the compatibilizing step, the crystalline resin can be uniformly dispersed in the obtained toner, and a high level of low-temperature fixability can be exhibited.
However, when the crystalline resin is crystallized by a heat treatment in a state where the crystalline resin is dissolved, domains of the crystalline resin grow greatly simultaneously with the formation of the phase separation structure accompanying the crystallization. As a result, the domain of the crystalline resin that is a low-resistance component is easily exposed on the toner surface, and the chargeability is deteriorated as described above.
Therefore, as a result of intensive studies, we conducted a solvent treatment process using a specific organic solvent to precipitate the crystalline resin, and the crystalline resin was sufficiently phase-separated from the amorphous resin in the toner. In addition, it has been found that a domain in which the crystalline resin is finely and uniformly dispersed in the toner can be formed.

<Solvent treatment step>
In the present invention, the solvent treatment step is a step of treating the compatibilized product with an organic solvent, and the organic solvent is a good solvent for the amorphous resin and a poor solvent for the crystalline resin.
In the compatibilizing step, the obtained compatibilized product is a good solvent for the amorphous resin, and by adding a specific organic solvent that is a poor solvent for the crystalline resin, the amorphous resin and This is a step in which a compatible crystalline resin is subjected to a precipitation treatment to obtain a solvent-treated product in which separation of a crystalline phase is induced.
By the solvent treatment step, the crystalline resin is sufficiently phase-separated from the amorphous resin, and the crystalline resin is uniformly dispersed in a state of fine domains. The reason for this is not clear, but is speculated as follows.
The solvent treatment step of the present invention is different from the conventional phase separation mechanism accompanying the crystal growth of the crystalline resin by heat treatment. This is because the heat treatment does not induce the phase separation and the crystal growth of the crystalline resin at the same time, but utilizes the difference in solubility between the amorphous resin and the crystalline resin in the organic solvent.
In other words, in the solvent treatment step, a good solvent for the amorphous resin and a poor solvent for the crystalline resin are added so that the amorphous resin is solubilized and is compatible with the amorphous resin. By crystallizing and precipitating only the resin, phase separation of the crystalline resin is realized. As a result, in the toner or the resin composition constituting the toner, a sufficient phase separation can be performed without greatly growing the domain of the crystalline resin.

In the solvent treatment step, the crystalline resin and the amorphous resin undergo phase separation as described above.
Therefore, the solvent-treated product obtained in the solvent treatment step preferably satisfies the following formula 2.
1.00> {(Wta−Wt0) / (Wr0 × Z / 100)}> 0 (Equation 2)
Wta: heat of fusion (J / g) derived from the crystalline resin at the first temperature rise in the measurement of the solvent-treated product using a differential scanning calorimeter (DSC)
Wt0: heat of fusion (J / g) derived from the crystalline resin at the first temperature rise in the measurement of the compatibilized product using a differential scanning calorimeter (DSC)
Wr0: heat of fusion (J / g) at the first temperature rise in the measurement of the crystalline resin using a differential scanning calorimeter (DSC)
Z: Content ratio (% by mass) of the crystalline resin in the compatibilized product

The measuring method of the differential scanning calorimeter (DSC) is as follows.
0.01 to 0.02 g of “compatibilized material (solid)”, “solvent-treated product (solid)”, or “crystalline resin” is precisely weighed in an aluminum pan and heated at a rate of 10 ° C. / In minutes, the temperature is raised from 0 ° C. to 200 ° C., and a DSC curve at the first temperature rise is obtained.
In the obtained DSC curve, the heat of fusion (J / g) is determined from the area surrounded by a straight line extending from the low-temperature-side baseline to the high-temperature side and the melting endothermic peak.

The molecule of the above (Formula 2) represents the heat of fusion (J / g) derived from the crystalline resin crystallized in the solvent treatment step, and the denominator corresponds to the heat of fusion (Wr0) of the crystal observed in the crystalline resin alone. The product of the content (Z) of the crystalline resin in the solubilized product, and the heat of fusion (J / g) when the crystalline resin contained in the solubilized product is crystallized in the same manner as the crystalline resin alone. means.
In the solvent-treated product obtained in the solvent treatment step, the crystalline resin and the amorphous resin were phase-separated, and in the compatibilized product obtained in the compatibilization step, they were compatible with the amorphous resin. The crystalline resin has crystallized. As a result, {(Wta−Wt0) / (Wr0 × Z / 100)} becomes larger than 0.
Further, by calculating the above {(Wta−Wt0) / (Wr0 × Z / 100)}, the amount of the crystalline resin crystallized and precipitated in the solvent treatment step, that is, the difference between the crystalline resin and the amorphous resin The degree of phase separation can be understood.
In the present invention, in order to further improve the chargeability, it is more preferable that 0.80> {(Wta−Wt0) / (Wr0 × Z / 100)}> 0.05 is satisfied, and 0.50> {(Wta) -Wt0) / (Wr0 × Z / 100)｝> 0.10.
In order to control the value of {(Wta−Wt0) / (Wr0 × Z / 100)}, for example, the amount of the organic solvent added in the solvent treatment step may be adjusted.

  In some cases, the solvent-treated product contains a release agent added as necessary, and a melting endothermic peak of the release agent or the like is observed. The melting endothermic peak of the release agent and the like and the melting endothermic peak derived from the crystalline resin are determined by using the above-described scanning scanning calorimetry method, by measuring the release agent and the like alone, and obtaining the obtained melting endothermic peak and the crystal. What is necessary is just to compare with the melting endothermic peak derived from the conductive resin. The release agent or the like may be obtained by extracting the release agent or the like from the compatibilized material by Soxhlet extraction using a hexane solvent, or using a release agent actually added.

<Organic solvent>
In the present invention, the organic solvent used in the solvent treatment step is not particularly limited as long as it is a good solvent for the amorphous resin and a poor solvent for the crystalline resin.
When the organic solvent is a good solvent for the amorphous resin and the crystalline resin, it is difficult to precipitate a crystalline resin compatible with the amorphous resin in the compatibilizing step.
On the other hand, when the solvent is poor for the amorphous resin and the crystalline resin, the solvent cannot penetrate into the amorphous resin because the solvent cannot penetrate into the amorphous resin. And precipitation of the crystalline resin cannot be induced.
The poor solvent in the present invention is a solvent having a resin solubility of less than 10 g / L at the processing temperature in the solvent processing step. On the other hand, a good solvent in the present invention is a solvent having a resin solubility of 100 g / L or more at the processing temperature in the solvent processing step.
That is, in the present invention, the good solvent of the amorphous resin is a solvent in which the solubility of the amorphous resin at the processing temperature of the solvent treatment step is 100 g / L or more, and the poor solvent of the crystalline resin is A solvent in which the solubility of the crystalline resin at the processing temperature in the solvent processing step is less than 10 g / L.
The larger the difference between the solubility of the organic solvent in the amorphous resin and the solubility of the organic solvent in the crystalline resin, the better. In view of the fact that the crystalline resin is precipitated in a situation where the crystalline resin and the amorphous resin are compatible as described above, the solubility of the crystalline resin at the processing temperature of the solvent treatment step is 5 g / L. The following is preferred.

In the present invention, the solubility of an amorphous resin and a crystalline resin in an organic solvent is calculated by the following method.
To 1 L of the organic solvent, an amorphous resin or a crystalline resin, a predetermined mass (1 to 200 g) was added, and the mixture was stirred for 12 hours under a processing temperature (for example, 25 ° C.) environment of the solvent processing step. The solubility is evaluated based on the turbidity and the presence or absence of a precipitate.
In addition, assuming that an organic solvent is added to an aqueous medium containing a compatibilized substance, when the solubility in water is low, phase separation may occur as an oil phase in the aqueous medium. When a compatibilized substance or the like is taken into the oil phase, coarse powder is likely to be generated. Therefore, the organic solvent is preferably a hydrophilic solvent. In the present invention, the hydrophilic solvent preferably has a solubility in water of 50 g / L or more at the treatment temperature in the solvent treatment step.

In the present invention, specific examples of the organic solvent include ethyl acetate, methyl acetate, methyl ethyl ketone, and isopropanol, but are not limited thereto.
When treating the compatibilized product with an organic solvent, it is preferable to treat the compatibilized product with sufficient stirring from the viewpoint of not generating coarse particles. Further, the treatment with the organic solvent is performed by dissolving or suspending the organic solvent in an aqueous medium containing a surfactant or the like with respect to a dispersion in which the compatibilized substance is dispersed in an aqueous medium containing a surfactant or the like. It is preferable to add it in a state where it has been added.
In the present invention, the amount of the organic solvent to be added in the solvent treatment step cannot be unconditionally defined because it depends on the types of the crystalline resin and the amorphous resin and the type of the organic solvent used.
As the amount added to the resin increases, the plasticization of the amorphous resin is promoted, and the solvent treatment step easily proceeds more quickly. However, when the addition amount is too large, the crystalline resin is easily dissolved in the organic solvent, and the crystalline resin tends to hardly precipitate. Further, the oil phase tends to undergo phase separation, and as a result, coarse powder is likely to be generated.
Therefore, the addition amount of the organic solvent in the solvent treatment step is preferably 1 part by mass or more and 500 parts by mass or less, more preferably 5 parts by mass or more and 250 parts by mass or less with respect to 100 parts by mass of the compatibilizer. It is more preferably from 5 parts by mass to 150 parts by mass. When an organic solvent having low solubility in water is used, the amount of the organic solvent added to the compatibilized product may be increased by diluting the concentration of the compatibilized product in the aqueous dispersion with ion-exchanged water or the like.

The temperature at the time of treating with an organic solvent in the solvent treatment step may be a temperature at which the solubility of the crystalline resin contained in the compatibilized product falls within the above range.
The higher the processing temperature, the lower the viscosity of the amorphous resin, and the more rapidly the crystallization of the crystalline resin is induced.However, the crystalline resin is easily dissolved in the same manner as the amount of the organic solvent added. Tends to be difficult to precipitate the conductive resin.
In the present invention, the temperature at the time of treatment with an organic solvent is preferably at least 20 ° C. lower than the melting point of the crystalline resin, more preferably at least 30 ° C. lower than the melting point of the crystalline resin, and 40 ° C. or lower than the melting point of the crystalline resin. A temperature lower than or equal to ° C is more preferable.
In the solvent treatment step, the time for treating with an organic solvent cannot be specified unconditionally because it depends on the treatment temperature and the amount of the organic solvent added, but generally it is preferably from 30 minutes to 10 hours.
Further, when the target crystal phase is separated, a solvent-treated product may be obtained by removing the organic solvent by cooling and reducing the pressure. In addition, the removal of the organic solvent is preferably performed at a temperature lower than the melting point of the crystalline resin by 30 ° C. or more, from the viewpoint of preventing the crystalline resin from dissolving and dissolving the crystalline resin and the amorphous resin again. A temperature lower by 40 ° C. or more than the melting point of the crystalline resin is more preferable, and a temperature lower by 50 ° C. or more than the melting point of the crystalline resin is still more preferable. Preferably, the temperature is lower.
Further, the solvent treatment step may be performed plural times to form a predetermined phase separation structure.

<Structural observation of toner cross section>
By going through the solvent treatment step, the crystalline resin is sufficiently phase-separated from the amorphous resin, and the crystalline resin is uniformly dispersed in fine domains. This dispersion state can be confirmed by observing the structure of the cross section of the toner using a transmission electron microscope (TEM).
First, a toner to be observed is sufficiently dispersed in a room-temperature curable epoxy resin, and a curing reaction is performed in an atmosphere at a temperature of 40 ° C. for one day or more to obtain a cured product in which the toner is embedded.
Next, using a microtome having diamond teeth, an ultrathin section is cut out from the cured product, and the obtained thin section is dyed with ruthenium tetroxide or osmium tetroxide.
Thereafter, using a transmission electron microscope (TEM), a photograph is taken at a magnification (approximately 10,000 times) in which the cross section of one toner enters a visual field.
By dyeing with ruthenium tetroxide or osmium tetroxide, components having different crystallinities contained in the toner are dyed with a contrast. Therefore, the domain of the crystalline resin contained in the toner can be identified by observation with a transmission electron microscope.
Among the obtained images of the toner cross section, 20 images of which the major axis of the toner cross section is 0.9 to 1.2 times the volume average particle diameter of the toner are photographed, and the taken image is analyzed by an image analyzer ( Image analysis by Nireco: Luzex AP) enables measurement and analysis of the phase separation structure between the amorphous resin and the crystalline resin, the domain diameter formed by the crystalline resin, and the degree of dispersion thereof.
In the toner obtained by the method of the present invention, the crystalline resin is subjected to a compatibilizing step as described above, and then precipitates in the toner by adding a poor solvent to form a domain. It is formed uniformly in the toner. The major axis of the needle-like crystals formed by the crystalline resin in the toner is preferably 0.5 μm or less, and as this size decreases, the interface with the amorphous resin increases, and the plasticizing effect in the fixing step increases. Become. Therefore, the major axis of the needle-like crystal is more preferably 0.3 μm or less. On the other hand, if the major axis of the needle crystal exceeds 0.5 μm, the needle crystal is likely to be exposed on the toner surface.

<Granulation process>
The method of the present invention may include a granulation step of obtaining particles having a volume average particle diameter of 3 μm or more and 10 μm or less. The granulation step is not particularly limited as long as particles having a volume average particle diameter of 3 μm or more and 10 μm or less can be obtained. It may be carried out after any of the above-mentioned compatibilizing step and solvent treatment step. For example, the following three embodiments can be preferably exemplified.

The method for measuring the volume average particle diameter of particles (aggregated particles, toner particles, etc.) is as follows.
Using a Coulter Multisizer III (manufactured by Coulter) as a measuring device, the measurement is performed according to the operation manual of the device.
The electrolyte may be an aqueous solution of about 1% sodium chloride using primary sodium chloride, but may be ISOTON-II (manufactured by Coulter Scientific Japan).
The specific measuring method is as follows.
0.1 to 5 mL of a surfactant (alkylbenzene sulfonate) as a dispersant is added to 100 to 150 mL of the electrolyte solution. 2 to 20 mg of a measurement sample (toner) is added to the electrolytic solution to which the dispersant has been added.
The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for 1 to 3 minutes using an ultrasonic disperser.
The volume of the particles having a particle size of 2.00 μm or more is measured from the obtained dispersion treatment liquid by the above-described measuring device equipped with an aperture tube of 100 μm as an aperture to calculate the volume distribution of the particles. Then, the volume average particle diameter of the particles (the median value of each channel is set as a representative value for each channel) is determined.
As the above channel, 2.00 μm or more and less than 2.52 μm; 2.52 μm or more and less than 3.17 μm; 3.17 μm or more and less than 4.00 μm; 4.00 μm or more and less than 5.04 μm; 6.35 μm to less than 8.00 μm; 8.00 μm to less than 10.08 μm; 10.08 μm to less than 12.70 μm; 12.70 μm to less than 16.00 μm; 16.00 μm to less than 20.20 μm; 13 channels of 25.40 μm or more and less than 32.00 μm; 32.00 μm or more and less than 40.30 μm are used.

(I) (granulation step-compatibilization step-solvent treatment step)
That is, the method of the present invention is a method for producing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin,
A granulation step containing the crystalline resin and the amorphous resin, and obtaining particles having a volume average particle diameter of 3 μm or more and 10 μm or less,
Compatibilizing step of compatibilizing the crystalline resin and the amorphous resin in the particles to obtain a compatibilized product, and
Including a solvent treatment step of treating the compatibilized product in the particles with an organic solvent,
The organic solvent is a good solvent for the amorphous resin and a poor solvent for the crystalline resin.

(Ii) (Compatibilizing Step-Granulating Step-Solvent Treatment Step)
That is, the method of the present invention is a method for producing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin,
A compatibilizing step of compatibilizing the crystalline resin and the amorphous resin to obtain a compatibilized product;
A granulation step containing the compatibilized material and obtaining particles having a volume average particle size of 3 μm or more and 10 μm or less, and
Including a solvent treatment step of treating the compatibilized product in the particles with an organic solvent,
The organic solvent is a good solvent for the amorphous resin and a poor solvent for the crystalline resin.

(Iii) (Compatibilization step-Solvent treatment step-Granulation step)
That is, the method of the present invention is a method for producing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin,
A compatibilizing step of compatibilizing the crystalline resin and the amorphous resin to obtain a compatibilized product;
A solvent treatment step of treating the compatibilized product with an organic solvent to obtain a solvent-treated product, and
Including the solvent-treated product, including a granulation step of obtaining particles having a volume average particle size of 3 μm or more and 10 μm or less,
The organic solvent is a good solvent for the amorphous resin and a poor solvent for the crystalline resin.

In the granulation step, when the organic solvent is added, coarse particles may be obtained or the particle diameter may be difficult to control due to the plasticization of the amorphous resin.
Therefore, when performing the solvent treatment step before the granulation step, it is preferable to sufficiently remove the organic solvent so that the organic solvent does not remain.
When the solvent treatment step is performed after the granulation step, there are a dry method and a wet method. The dry method is a method in which the particles obtained in the granulation step are exposed while being circulated in an air stream containing the above-mentioned organic solvent gas.
The wet method is a method in which the particles obtained in the granulation step are dispersed in an aqueous medium containing a surfactant by a known method, and then the organic solvent is added.
The wet method is preferable because the change in the particle diameter due to the addition of the organic solvent is small.
On the other hand, when the compatibilizing step and the solvent treatment step are performed before the granulating step as described in (iii) above, the granulating step is performed so that the crystalline resin and the amorphous resin do not become compatible again. Is preferably performed at a temperature lower than the melting point of the crystalline resin.
Therefore, the solvent treatment step is preferably performed after the granulation step, and the particles obtained in the granulation step are dispersed in an aqueous medium containing a surfactant, and the organic solvent is added. Is more preferable.

The compatibilizing step and the solvent treatment step, and the granulating step can be performed by a known method for producing a toner such as a suspension polymerization method, a kneading and pulverizing method, an emulsion aggregation method, and a dissolution suspension method, It is not limited to either method.
Hereinafter, the application of the compatibilization step, the solvent treatment step, or the granulation step in the suspension polymerization method, the kneading and pulverizing method, and the emulsion aggregation method will be specifically exemplified, but the application is not limited thereto.
<Suspension polymerization method>
In the suspension polymerization method, the polymerizable monomer and the crystalline resin constituting the amorphous resin, and, if necessary, a colorant, and other materials such as a release agent are uniformly dissolved or dispersed to form a polymerizable polymer. Obtain a monomer composition. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer as necessary using a suitable stirrer. Thereafter, particles having a desired particle size are obtained by polymerizing the polymerizable monomer (granulation step). The toner can be obtained by filtering, washing and drying the obtained particles by a known method. Thereafter, if necessary, inorganic particles such as silica, alumina, titania, and calcium carbonate, and resin particles such as a vinyl resin, a polyester resin, and a silicone resin are added by applying a shearing force in a dry state. Is also good. These inorganic fine particles and resin fine particles function as external additives such as a flow aid and a cleaning aid.
In the suspension polymerization method, the compatibilization step and the solvent treatment step may be performed after the granulation step.
<Kneading and pulverizing method>
In the kneading and pulverizing method, first, a resin, which is a constituent material of the toner, and a releasing agent, a coloring agent, and other additives that are added as necessary are sufficiently mixed, and a known heat kneading method such as a heating roll or a kneader is used. Is melt-kneaded using a mixer (kneading step). Thereafter, the toner is mechanically pulverized to a desired toner particle diameter (pulverizing step), and classified to obtain a desired particle size distribution (classifying step), thereby producing a toner.
The average circularity of the toner obtained by the kneading and pulverizing method is usually less than 0.955 and the shape is often distorted. Therefore, if necessary, the toner obtained by the kneading and pulverizing method is subjected to a known method, for example, a water dispersion heating method in which the toner is dispersed in water and heated, or a heat treatment in which the toner is put in a hot air flow and heated. The method may include a step of forming a heat sphere by the method.

In the kneading and pulverizing method, the granulating step corresponds to a pulverizing step and a classification step of obtaining resin particles having a volume average particle diameter of 3 μm or more and 10 μm or less.
Further, the granulation step may be performed after the compatibilizing step and the solvent processing step, may be performed between the compatibilizing step and the solvent processing step, or may be performed before the compatibilizing step and the solvent processing step. You can also. Examples of each case are described below.
(1) When the granulating step is performed after the compatibilizing step and the solvent treatment step, the compatibilizing step is to bring the resin composition containing the crystalline resin and the amorphous resin to a temperature higher than the melting point of the crystalline resin. This is a kneading step of heating, melting and kneading.
In the kneading step, the crystalline resin and the amorphous resin present in the resin composition constituting the toner are made compatible with each other by heating to a temperature higher than the melting point of the crystalline resin to obtain a compatibilized product.
Thereafter, a solvent treatment step of treating the compatibilized product with an organic solvent is continuously performed.
In the solvent treatment step, the above organic solvent is preferably added to the compatibilized product obtained in the compatibilization step, and then the mixture is kneaded again.
(2) When the granulation step is performed between the compatibilizing step and the solvent processing step, in the solvent processing step, the resin particles that have been subjected to the compatibilizing step and the pulverizing step and the classifying step, which are the granulating steps, are subjected to the above-mentioned organic treatment. It is preferable to circulate and expose in a gas stream containing a solvent gas (dry method). Alternatively, the organic solvent may be added to a dispersion obtained by dispersing the resin particles in an aqueous medium containing a surfactant by a known method, followed by stirring (wet method).
(3) When the granulating step is performed before the compatibilizing step and the solvent treating step, the compatibilizing step refers to a method in which the toner obtained through the kneading step, the pulverizing step, and the classifying step is subjected to a known method, for example, This is a step of heating the crystalline resin to a temperature higher than the melting point of the crystalline resin to form a thermal sphere by a water dispersion heating method in which the toner is dispersed in water and heated, or a heat treatment method in which the toner is put into a hot air stream and heated.
In the step of forming the thermal sphere, the crystalline resin is heated to a temperature equal to or higher than the melting point of the crystalline resin, so that the crystalline resin and the amorphous resin present in the resin constituting the toner are compatibilized to obtain a compatibilized product.
Thereafter, in the solvent treatment step, for example, the organic solvent is added to a dispersion obtained by dispersing the compatibilized substance obtained in the compatibilization step in an aqueous medium containing a surfactant by a known method, It is good to stir.

Hereinafter, each step of the kneading and pulverizing method will be further described.
<Kneading process>
Melt kneading of the constituent materials of the toner can be performed using a known heat kneading machine such as a heating roll or a kneader. In the kneading step, it is preferable that the constituent materials of the toner are sufficiently mixed in advance using a mixer.
As a mixing machine, a Henschel mixer (Mitsui Mining); a super mixer (Kawata); a ribocorn (Okawara Seisakusho); a Nauta mixer, a turbulizer, a cyclomix (Hosokawa Micron); Pacific Kiko Co., Ltd.); Ledige mixer (Matsubo Co., Ltd.).
As the heat kneader, KRC kneader (manufactured by Kurimoto Iron Works); bus co-kneader (manufactured by Buss); TEM extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works) PCM kneader (Ikegai Iron Works); three-roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); Kneedex (manufactured by Mitsui Mining); MS type pressure kneader; A Banbury mixer (manufactured by Kobe Steel Ltd.).
<Pulverization process>
The pulverizing step, after cooling the kneaded material obtained in the kneading step to reach a pulverizable hardness, impact plate type jet mill, fluidized bed type jet mill, and a known pulverizer such as a rotary mechanical mill, This is a step of mechanically pulverizing until the particle diameter of the toner is reached. From the viewpoint of crushing efficiency, it is preferable to use a fluidized bed jet mill as the crusher.
Examples of the pulverizer include a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS-type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic), a cross jet mill (manufactured by Kurimoto Tekkosho); Nisso Engineering Co., Ltd.); SK Jet O Mill (Seisin Enterprise); Kryptron (Kawasaki Heavy Industries); Turbo Mill (Turbo Kogyo); Super Rotor (Nissin Engineering Co.). .
<Classification process>
The classification step is a step of classifying the finely pulverized product obtained in the above-mentioned pulverization step to obtain a toner having a desired particle size distribution.
As a classifier used for classification, a known device such as an air classifier, an inertial classifier, and a sieve classifier can be used. Specifically, Crasheal, Micron Classifier, Spedick Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nisshin Engineering); micron separator, turboflex (ATP), TSP separator (manufactured by Hosokawa Micron) Elbow jet (manufactured by Nippon Steel Mining), dispersion separator (manufactured by Nippon Pneumatic), and YM microcut (manufactured by Yaskawa Shoji).
In the toner produced through the above steps, if necessary, inorganic fine particles such as silica, alumina, titania, and calcium carbonate, and resin fine particles such as a vinyl resin, a polyester resin, and a silicone resin are sheared in a dry state. You may add by applying a force. These inorganic fine particles and resin fine particles function as external additives such as a flow aid and a cleaning aid.

<Emulsion aggregation method>
Emulsion aggregation method is to prepare in advance an aqueous dispersion of fine particles composed of toner constituent materials, which is sufficiently small for the target particle diameter, and aggregate the fine particles in an aqueous medium until the particle diameter of the toner is reached. This is a method for producing a toner by fusing a resin by heating.
That is, in the emulsification aggregation method, a dispersion step of preparing a fine particle dispersion liquid composed of the constituent material of the toner, an aggregation step of aggregating the fine particles composed of the constituent material of the toner and controlling the particle diameter until the particle diameter of the toner is obtained, The toner is manufactured through a fusion step of fusing the resin contained in the obtained aggregated particles and a subsequent cooling step.
In the emulsion aggregation method, the above-mentioned granulation step corresponds to an aggregation step of obtaining resin particles having a volume average particle diameter of 3 μm or more and 10 μm or less.
Further, the granulation step (aggregation step) may be performed after the compatibilization step and the solvent treatment step, may be performed between the compatibilization step and the solvent treatment step, or may be performed before the compatibilization step and the solvent treatment step. It can also be implemented. Examples of each case are described below.
(1) When the granulation step (aggregation step) is performed after the compatibilization step and the solvent treatment step, or when the granulation step (aggregation step) is performed between the compatibilization step and the solvent treatment step. Is, in an organic solvent capable of dissolving the crystalline resin and the amorphous resin, dissolve the crystalline resin and the amorphous resin, using a dispersant known stirrer, emulsifier, and disperser This is a step of obtaining a compatibilized product (composite fine particles) in which the crystalline resin and the amorphous resin are compatible by mixing with a suitable mixer (this step also serves as an emulsification step).
By dissolving the crystalline resin and the amorphous resin in an organic solvent capable of dissolving the crystalline resin and the amorphous resin, the compatibilization between the crystalline resin and the amorphous resin is induced, and then formed. The crystalline resin is uniformly dispersed in the composite fine particles.
In the solvent treatment step, a dispersion obtained by dispersing the compatibilized product (composite fine particles) in an aqueous medium containing a surfactant by a known method is a good solvent for the amorphous resin, and It is preferable to add the above-mentioned organic solvent, which is a poor solvent for the hydrophilic resin, and stir.
When the granulation step (aggregation step) is performed after the compatibilization step and the solvent treatment step, the granulation step (aggregation step) is performed so that the crystalline resin and the amorphous resin are not compatibilized again in the subsequent steps. And the coalescing step may be performed with less than the crystalline resin.
When the specific organic solvent added in the solvent treatment step remains in the aqueous dispersion containing the composite fine particles, coarse particles are likely to be generated in the subsequent granulation step (aggregation step) and fusion step. Therefore, the above-mentioned specific organic solvent is preferably sufficiently removed.
(2) When the granulation step (aggregation step) is performed before the compatibilizing step and the solvent treatment step: The compatibilizing step is a toner obtained by aggregating fine particles of a crystalline resin and fine particles of an amorphous resin. This is a fusion step in which the aggregated particles having a particle size are fused by heating to a temperature higher than the melting point of the crystalline resin. In the fusion step, the crystalline resin and the amorphous resin present in the aggregated particles are made compatible with each other by heating to a temperature equal to or higher than the melting point of the crystalline resin to obtain a compatibilized product.
Thereafter, in the solvent treatment step, the organic solvent is preferably added to the aqueous dispersion containing the compatibilized substance, followed by stirring.

Hereinafter, each step of the emulsion aggregation method will be further described.
<Dispersion process>
The aqueous dispersion of the fine particles of the amorphous resin and the crystalline resin can be prepared by a known method, but is not limited to these methods. Known methods include, for example, emulsion polymerization, self-emulsification, phase inversion emulsification in which the resin is emulsified by adding an aqueous medium to a resin solution dissolved in an organic solvent, or without using an organic solvent. And a forced emulsification method in which the resin is forcibly emulsified by high-temperature treatment in an aqueous medium.
Specifically, a non-crystalline resin or a crystalline resin is dissolved in an organic solvent in which these are dissolved, and a surfactant and a basic compound are added. Then, while stirring with a homogenizer or the like, an aqueous medium is slowly added to precipitate resin fine particles. Thereafter, by heating or reducing the pressure to remove the solvent, an aqueous dispersion of resin fine particles is prepared. As the organic solvent used to dissolve the resin, any organic solvent that can dissolve the resin can be used, but an organic solvent that forms a uniform phase with water, such as tetrahydrofuran, may be used. It is preferable from the viewpoint of suppressing the generation of coarse powder.
The surfactant used at the time of the emulsification is not particularly limited, for example, a sulfate-based, sulfonate-based, carboxylate-based, phosphate-based, soap-based anionic surfactants Amine salts, quaternary ammonium salts and the like; cationic surfactants; polyethylene glycols, alkylphenol ethylene oxide adducts, and non-ionic surfactants such as polyhydric alcohols. These surfactants may be used alone or in combination of two or more.
Examples of the basic compound used in the emulsification include an inorganic base such as sodium hydroxide and potassium hydroxide; and an organic base such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The bases may be used alone or in combination of two or more.
The 50% particle size (d50) based on the volume distribution of the fine particles of the amorphous resin is preferably 0.05 to 1.0 μm, and more preferably 0.05 to 0.4 μm.
By adjusting the 50% particle size (d50) based on the volume distribution to the above range, it becomes easy to obtain toner particles having a volume average particle size of 3 μm or more and 10 μm or less, which are appropriate as toner particles.
The 50% particle size (d50) based on the volume distribution of the fine particles of the crystalline resin is preferably from 0.05 to 0.5 μm, from the viewpoint of suppressing generation of coarse particles in the aggregation step, and from 0.05 to 0.5 μm. .3 μm is more preferable.
For the measurement of the 50% particle size (d50) based on the volume distribution, a dynamic light scattering type particle size distribution meter (Nanotrack UPA-EX150: manufactured by Nikkiso Co., Ltd.) is used.

The aqueous dispersion of the coloring agent fine particles used as necessary can be prepared by the following known methods, but is not limited to these methods.
It can be prepared by mixing a colorant, an aqueous medium and a dispersant with a known mixer such as a stirrer, emulsifier and disperser. Known dispersants such as surfactants and polymer dispersants can be used here.
Both the surfactant and the polymer dispersant can be removed in the washing step described later, but a surfactant is preferred from the viewpoint of washing efficiency.
Examples of the surfactant include anionic surfactants such as sulfate, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; Nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols are included.
Among these, a nonionic surfactant or an anionic surfactant is preferable. Further, a nonionic surfactant and an anionic surfactant may be used in combination. These surfactants may be used alone or in combination of two or more. The concentration of the surfactant in the aqueous medium is preferably 0.5 to 5% by mass.
The content of the colorant fine particles in the aqueous dispersion is not particularly limited, but is preferably 1 to 30% by mass based on the total mass of the aqueous dispersion of colorant fine particles.
Further, from the viewpoint of the dispersibility of the colorant in the finally obtained toner, the 50% particle size (d50) based on the volume distribution is 0.5 μm or less from the viewpoint of the dispersibility of the colorant in the finally obtained toner. It is preferred that For the same reason, the 90% particle size (d90) based on the volume distribution is preferably 2 μm or less. Incidentally, the dispersion particle size of the colorant fine particles dispersed in the aqueous medium,
It is measured by a dynamic light scattering particle size distribution analyzer (Nanotrack UPA-EX150: manufactured by Nikkiso Co., Ltd.).
Known mixers used for dispersing the colorant in the aqueous medium, mixers such as emulsifiers, and dispersers include an ultrasonic homogenizer, a jet mill, a pressure homogenizer, a colloid mill, a ball mill, a sand mill, and Paint shaker. These may be used alone or in combination.

The aqueous dispersion of release agent fine particles used as necessary can be prepared by the following known methods, but is not limited to these methods.
An aqueous dispersion of release agent fine particles is prepared by adding a release agent to an aqueous medium containing a surfactant, heating the release agent to a temperature higher than the melting point of the release agent, and having a strong shearing ability (for example, M Technic Co., Ltd.). Manufactured by the company “Clearmix W Motion” manufactured by Nippon Kayaku Co., Ltd.) or a pressure discharge type dispersing machine (eg, “Gaulin Homogenizer” manufactured by Gorin) and then cooled to a temperature lower than the melting point.
The dispersed particle diameter of the release agent fine particles in the aqueous dispersion liquid is preferably such that the 50% particle diameter (d50) based on volume distribution is 0.03 to 1.0 μm, and 0.1 to 0.5 μm. Is more preferred. Further, it is preferable that there are no coarse particles of 1 μm or more.
When the dispersed particle diameter of the release agent fine particles is within the above range, the release agent at the time of fixing becomes good, the hot offset temperature can be increased, and the occurrence of filming on the photoconductor is reduced. It can be suppressed. The dispersed particle size of the release agent fine particles dispersed in the aqueous medium is measured by a dynamic light scattering type particle size distribution analyzer (Nanotrack UPA-EX150: manufactured by Nikkiso Co., Ltd.).

<Aggregation step>
In the aggregation step, the aqueous dispersion of the amorphous resin fine particles, the aqueous dispersion of the crystalline resin fine particles, and the aqueous dispersion of the release agent fine particles, and the aqueous dispersion of the colorant fine particles as necessary are mixed. A mixed solution is prepared. Next, the fine particles contained in the prepared mixture are aggregated to form aggregated particles having a desired particle size. At this time, an aggregating agent is added and mixed, and if necessary, heating and / or mechanical power is appropriately applied to form aggregated particles in which resin fine particles, colorant fine particles, and release agent fine particles are aggregated.
As the coagulant, it is preferable to use a coagulant containing a divalent or higher valent metal ion. A coagulant containing a divalent or higher metal ion has a high cohesive force, and when added in a small amount, an acidic polar group of resin fine particles, an aqueous dispersion of resin fine particles, an aqueous dispersion of colorant fine particles, and a release agent. The ionic surfactant contained in the aqueous dispersion of fine particles can be ionized neutralized. As a result, the resin fine particles, the colorant fine particles, and the release agent fine particles are aggregated by the effects of salting out and ionic crosslinking.
Examples of the coagulant containing a divalent or higher valent metal ion include a divalent or higher valent metal salt or a polymer of a metal salt. Specifically, divalent inorganic metal salts such as calcium chloride, calcium nitrate, magnesium chloride, magnesium sulfate, and zinc chloride, iron (III) chloride, iron (III) sulfate, aluminum sulfate, and aluminum chloride Trivalent metal salts, and inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide, but are not limited thereto. These may be used alone or in combination of two or more.
The coagulant may be added in any form of a dry powder or an aqueous solution dissolved in an aqueous medium, but is preferably added in the form of an aqueous solution in order to cause uniform coagulation.
The addition and mixing of the flocculant are preferably performed at a temperature equal to or lower than the glass transition temperature of the resin contained in the mixture. Aggregation proceeds uniformly by mixing under this temperature condition. Mixing of the flocculant into the mixture can be performed using a known mixing device such as a homogenizer and a mixer.
As described above, the average particle diameter of the aggregated particles formed in the aggregation step is preferably controlled so that the volume average particle diameter is 3 μm or more and 10 μm or less. The particle size of the aggregated particles can be easily controlled by appropriately adjusting the temperature, the solid concentration, the concentration of the aggregating agent, and the conditions of stirring.
Further, by adding resin fine particles for forming a shell phase to the dispersion of the aggregated particles obtained in the above aggregation step, a shell attaching step of attaching the resin fine particles to the surface of the aggregated particles, and The toner particles having a core-shell structure can be manufactured by subjecting the aggregated particles having the particles adhered to the surface to a fusion step described below. The resin fine particles for forming the shell phase to be added here may be resin fine particles having the same structure as the resin contained in the aggregated particles or resin fine particles having a different structure.

<Fusion process>
In the fusion step, an aggregation terminator is added to the dispersion containing the aggregated particles obtained in the aggregation step under the same stirring as in the aggregation step. As the aggregation terminator, a basic compound that shifts the equilibrium of the acidic polar group of the resin fine particles to the dissociation side and stabilizes the aggregated particles; A chelating agent that stabilizes aggregated particles by dissociation and forming a coordinate bond with a metal ion. Among these, a chelating agent having a greater effect of stopping aggregation is preferable.
After the dispersion state of the aggregated particles in the dispersion is stabilized by the action of the aggregation terminator, the aggregated particles are fused by heating to a temperature equal to or higher than the glass transition temperature of the amorphous resin.
When the compatibilizing step is performed simultaneously with the fusion step, the aggregated particles are fused by heating to a temperature equal to or higher than the melting point of the crystalline resin.
Further, as described above, when the fusion step is performed after the compatibilizing step and the solvent processing step are performed, the melting point of the crystalline resin is adjusted so that the crystalline resin and the amorphous resin do not become compatible again. It is good to carry out in less than.
The chelating agent is not particularly limited as long as it is a known water-soluble chelating agent. Specifically, oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, and their sodium salts; iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA); A sodium salt of
The chelating agent coordinates the metal ions of the coagulant present in the dispersion of the aggregated particles, thereby changing the environment in the dispersion from an unstable and easily aggregated state to an electrostatically dispersed state. It can be changed to a state that is stable and hard to cause further aggregation. Thereby, further aggregation of the aggregated particles in the dispersion liquid can be suppressed, and the aggregated particles can be stabilized.
The chelating agent is preferably an organic metal salt having a trivalent or higher carboxylic acid, since it is effective even with a small amount of addition, and toner particles having a sharp particle size distribution can be obtained.
In addition, the addition amount of the chelating agent is preferably 1 to 30 parts by mass, and more preferably 2.5 to 15 parts by mass, based on 100 parts by mass of the resin particles, from the viewpoint of achieving both the stability from the aggregation state and the washing efficiency. Is more preferable.
A toner can be obtained by washing, filtering, drying, etc., the particles produced through the above-mentioned fusion step. Thereafter, if necessary, inorganic particles such as silica, alumina, titania, and calcium carbonate, and resin particles such as a vinyl resin, a polyester resin, and a silicone resin are added by applying a shearing force in a dry state. Is also good. These inorganic fine particles and resin fine particles function as external additives such as a flow aid and a cleaning aid.

Subsequently, the constituent materials according to the present invention will be described.
<Crystalline resin>
In the present invention, the crystalline resin is not particularly limited as long as it has crystallinity and is compatible with the amorphous resin, and can be appropriately selected depending on the purpose.
The crystalline resin shows a melting endothermic peak in differential scanning calorimetry using a differential scanning calorimeter (DSC).
Examples of the crystalline resin include a crystalline polyester resin, a crystalline polyurethane resin, a crystalline polyurea resin, a crystalline polyamide resin, a crystalline polyether resin, a crystalline vinyl resin, and a modified crystalline resin. These may be used alone or in combination of two or more.
Among these, a crystalline polyester resin is preferred from the viewpoint of melting point and mechanical strength.
The structure of the crystalline polyester resin is not particularly limited, but examples include a structure obtained by polycondensing at least one dicarboxylic acid component and at least one diol component.
Specific examples of the diol include the following. From the viewpoint of the ester group concentration and the melting point described below, a linear aliphatic diol having 4 to 20 carbon atoms is preferable.
Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Diol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-ico Examples include diols such as sundiol, 2-methyl-1,3-propanediol, cyclohexanediol, and cyclohexanedimethanol. These may be used alone or in combination of two or more.
It is also possible to use a trivalent or higher alcohol, such as glycerin, pentaerythritol, hexamethylolmelamine, and hexaethylolmelamine. These may be used alone or in combination of two or more.
Specific examples of the dicarboxylic acid include the following, and from the viewpoint of the ester group concentration and the melting point described below, a linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is preferable.
Oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, Alicyclic dicarboxylic acids such as 1,1-cyclopentenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid; phthalic acid, isophthalic acid Acid, terephthalic acid, p-phenylene diacetate, m-fe Ren diacetate, p- phenylenediamine propionitrile Nick acid, m- phenylenediamine propionitrile Nick acid, naphthalene-1,4-dicarboxylic acid, aromatic dicarboxylic acids such as naphthalene-1,5-dicarboxylic acid. These may be used alone or in combination of two or more.
It is also possible to use a trivalent or higher polycarboxylic acid, such as trimellitic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid, and trivalent or higher polycarboxylic acid. And polyvalent carboxylic acids. These may be used alone or in combination of two or more.

As described above, it is generally known that a crystalline resin has a lower volume resistance than a conventional amorphous resin. For this reason, the present inventors consider as follows.
In general, a crystalline resin has a crystal structure in which molecular chains show a regular arrangement.From a macroscopic viewpoint, it is said that a molecular resin maintains a state where molecular motion is restricted in a temperature region lower than a melting point. Conceivable. However, when viewed from a microscopic point of view, the crystalline resin is not entirely composed of a crystal structure part, and the molecular structure shows a regular arrangement of molecular chains and has a crystal structure, and the other amorphous structure has an amorphous structure. Part.
In the case of a crystalline polyester resin having a melting point in a range normally used in toner, the glass transition temperature (Tg) of the crystalline polyester resin is much lower than room temperature. It is considered that the amorphous structure has caused molecular motion. In such an environment where the molecular mobility of the resin is high, it is possible to transfer charges via an ester bond or the like which is a polar group, and as a result, it is considered that the volume resistance of the resin decreases.
Therefore, it is presumed that the volume resistance can be increased by suppressing the concentration of the ester group, which is a polar group, to be low. Therefore, a crystalline polyester resin having a low ester group concentration is preferably used.
The value of the ester group concentration is mainly determined by the types of the diol component and the dicarboxylic acid component, and can be designed to be a low value by selecting one having a large carbon number.
However, when the ester group concentration is designed to be low, the compatibility with the amorphous resin described later may be reduced, or the melting point of the obtained crystalline polyester resin may be increased.

The weight average molecular weight (Mw) of the crystalline resin measured by gel permeation chromatography is preferably 5,000 or more and 50,000 or less, more preferably 5,000 or more and 20,000 or less.
When the weight average molecular weight (Mw) of the crystalline resin satisfies the above range, the resin strength and low-temperature fixability of the toner can be further improved.
The weight average molecular weight (Mw) of the crystalline resin can be easily controlled by various known production conditions of the crystalline resin.
The weight average molecular weight (Mw) of the crystalline resin is measured using gel permeation chromatography (GPC) as follows.
Special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added to o-dichlorobenzene for gel chromatography so as to have a concentration of 0.10% by mass, and dissolved at room temperature. The crystalline resin and o-dichlorobenzene to which the above BHT is added are placed in the sample bottle, and heated on a hot plate set at 150 ° C. to dissolve the crystalline resin.
When the crystalline resin is melted, put it in a pre-heated filter unit and place it on the main unit. What passed through the filter unit is used as a GPC sample.
The sample solution is adjusted so that the concentration is about 0.15% by mass.
Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: High temperature RI
Column: TSKgel GMHHR-H HT 2 stations (Tosoh Corporation)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatography (0.10% by mass of BHT added)
Flow rate: 1.0ml / min
Injection volume: 0.4ml
When calculating the molecular weight of the crystalline resin, a standard polystyrene resin (trade name: “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-20, 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation).

  In the present invention, the melting point of the crystalline resin is preferably from 50 ° C. to 100 ° C. from the viewpoints of low-temperature fixability and storage stability. When the melting point is 100 ° C. or less, the low-temperature fixability is further improved. Further, when the melting point is 90 ° C. or less, the low-temperature fixability is further improved. On the other hand, when the melting point is lower than 50 ° C., the storage stability tends to decrease.

The melting point of the crystalline resin can be measured using a differential scanning calorimeter (DSC).
Specifically, a sample of 0.01 to 0.02 g is precisely weighed in an aluminum pan, and the temperature is raised from 0 ° C. to 200 ° C. at a rate of 10 ° C./min to obtain a DSC curve.
From the obtained DSC curve, the peak temperature of the melting endothermic peak is defined as the melting point.
Also, the melting point of the crystalline resin present in the toner can be measured by the same method. At that time, the melting point due to the release agent present in the toner may be observed. The determination of the melting point of the release agent and the melting point of the crystalline resin can be obtained by extracting the release agent from the toner by Soxhlet extraction using a hexane solvent, performing the scanning calorimetry of the release agent alone by the above method. The comparison is made between the melting point of the toner and the melting point of the toner.

  In the present invention, the crystalline resin is preferably contained in the toner in an amount of 10% by mass or more and 40% by mass or less. When the crystalline resin is contained in the toner in an amount of 10% by mass or more, more excellent low-temperature fixability is exhibited. That is, when the crystalline resin is contained in the toner in an amount of 10% by mass or more and 40% by mass or less, both low-temperature fixability and chargeability can be achieved at a high level.

<Amorphous resin>
In the present invention, the amorphous resin is not particularly limited as long as it is a resin compatible with the crystalline resin, and can be appropriately selected from known resins generally used for toner.
Specifically, the following polymers or resins can be exemplified.
Polystyrene, poly-p-chlorostyrene, and a homopolymer of styrene such as polyvinyltoluene and a substituted product thereof; a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, Styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl Styrene copolymers such as ether copolymer, styrene-vinyl methyl ketone copolymer, and styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, modified phenol resin, modified maleic resin, acrylic resin, Methacrylic resin, Vinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone - indene resins, and petroleum resins.
Among them, a polyester resin having high compatibility with crystalline polyester, which is a preferable structure among crystalline resins, and having excellent strength even with a low molecular weight is preferable.
As the polyester resin, a resin obtained by condensation polymerization of an alcohol monomer and a carboxylic acid monomer is used.
Examples of the alcohol monomer include the following. Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2. 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) alkylene oxide adducts of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, sorbitol, 1,2 , 3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropane Triol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene.
On the other hand, examples of the carboxylic acid monomer include the following.
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; alkyl groups having 6 to 18 carbon atoms Or succinic acid or an anhydride thereof substituted with an alkenyl group; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid, or anhydrides thereof.
In addition, the following monomers can be used.
Polyhydric alcohols such as oxyalkylene ethers of novolak type phenol resins; and polycarboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and anhydrides thereof.
Among them, particularly, a bisphenol derivative represented by the following general formula (1) is used as a dihydric alcohol monomer component, and a carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof ( For example, a resin obtained by condensation polymerization of fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid as carboxylic acid monomer components is preferable.

（式中、Ｒはエチレン基又はプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつ、ｘ＋ｙの平均値は２〜１０である。）

(In the formula, R represents an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

The glass transition temperature of the amorphous resin is preferably 30 ° C. or more and 80 ° C. or less.
When the glass transition temperature is 30 ° C. or higher, storage stability is improved. Further, in a high-temperature and high-humidity environment, a decrease in resistance due to the molecular motion of the resin is less likely to be induced, so that the chargeability is also improved.
On the other hand, when the glass transition temperature is 80 ° C. or lower, the low-temperature fixability is improved.
Further, the glass transition temperature is more preferably 40 ° C. or more from the viewpoint of storage stability. On the other hand, the glass transition temperature is more preferably 70 ° C. or less from the viewpoint of low-temperature fixability.
The glass transition temperature (Tg) can be measured using a differential scanning calorimeter (manufactured by METTLER TOLEDO: DSC822 / EK90).
Specifically, a sample of 0.01 to 0.02 g is precisely weighed in an aluminum pan, and the temperature is raised from 0 ° C. to 200 ° C. at a rate of 10 ° C./min. Subsequently, the temperature is cooled from 200 ° C. to −100 ° C. at a temperature lowering rate of 10 ° C./min, and the temperature is raised again from −100 ° C. to 200 ° C. at a temperature increasing rate of 10 ° C./min to obtain a DSC curve.
From the obtained DSC curve, the temperature at the intersection of a straight line obtained by extending the low-temperature-side baseline to the high-temperature side and a tangent drawn at a point where the slope of the curve of the step change portion of the glass transition becomes the maximum is calculated. The transition temperature.

In the present invention, the softening temperature (Tm) of the amorphous resin is preferably from 70 ° C to 150 ° C, more preferably from 80 ° C to 140 ° C, and from 80 ° C to 130 ° C. Is more preferred.
When the softening temperature (Tm) is within the above-mentioned temperature range, a good balance between the blocking resistance and the offset resistance is achieved, and the penetration of the toner melt component into the paper during fixing at a high temperature is moderate. And good surface smoothness is obtained.
In the present invention, the softening temperature (Tm) of the amorphous resin can be measured by using a capillary rheometer of constant load extrusion type “flow characteristic evaluation apparatus flow tester CFT-500D” (manufactured by Shimadzu Corporation).
In addition, CFT-500D applies a constant load by a piston from the top, melts the measurement sample filled in the cylinder while raising the temperature, and extrudes it through a capillary hole at the bottom of the cylinder. It is a device that can graph the flow curve from temperature (° C).
In the present invention, the “melting temperature in the 法 method” described in the manual attached to the “flow characteristic evaluation device flow tester CFT-500D” is defined as the softening temperature (Tm).
The melting temperature in the 1/2 method is calculated as follows.
First, a half of the difference between the piston descent amount at the time when the outflow ends (outflow end point, Smax) and the piston descent amount at the time of the outflow start (lowest point, Smin) is determined. (This is X. X = (Smax-Smin) / 2). Then, the temperature of the flow curve when the piston descending amount is the sum of X and Smin is defined as the melting temperature in the 1/2 method.
The measurement sample was prepared by subjecting 1.2 g of the amorphous resin to a pressure of 60 MPa at 10 MPa using a tableting compression machine (for example, a standard manual Newton press NT-100H, manufactured by NPA System) in an environment of 25 ° C. A cylinder having a diameter of 8 mm formed by compression molding for 2 seconds is used.
The specific operation in the measurement is performed according to the manual attached to the device.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rise start temperature: 60 ° C
Ultimate temperature: 200 ° C
Measurement interval: 1.0 ° C
Heating rate: 4.0 ° C / min
Piston cross-sectional area: 1.000cm ²
Test load (piston load): 5.0 kgf
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

The amorphous resin preferably has an ionic group such as a carboxylic acid group, a sulfonic acid group, or an amino group in the resin skeleton, and more preferably has a carboxylic acid group.
The acid value of the amorphous resin is preferably from 3 to 35 mgKOH / g, more preferably from 8 to 25 mgKOH / g.
When the acid value of the amorphous resin is within the above range, a good charge amount can be obtained both in a high humidity environment and a low humidity environment. The acid value is the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids and the like contained in 1 g of the sample. The measuring method is measured according to JIS-K0070.

In the present invention, the crystalline resin and the amorphous resin are compatible combinations.
In order to select a compatible combination of a crystalline resin and an amorphous resin, the following should be considered.
(1) As the crystalline resin and the amorphous resin, those having the same resin skeleton are selected.
For example, the crystalline resin is a crystalline polyester resin, and the amorphous resin is an amorphous polyester resin. The crystalline resin is a crystalline acrylic resin, and the amorphous resin is an amorphous acrylic resin.
(2) Further, the absolute value (ΔSP value) of the difference between the solubility parameter value (SP value) of the crystalline resin and the amorphous resin used is preferably 0.00 or more and 1.70 or less. It is more preferably from 0.000 to 1.65, and even more preferably from 0.00 to 1.60.
The SP value can be obtained using the Fedors equation. Here, for the values of Δei and Δvi, see “Evaporation energy and molar volume (25 ° C.) of atoms and atomic groups” according to Table 3-9 of “Basic Science of Coating”, pp. 54-57, 1986 (Maki Shoten). did.
Formula: δi = [Ev / V] ^1/2 = [Δei / Δvi] ^1/2
Ev: Evaporation energy V: Molar volume Δei: Evaporation energy of atom or atomic group of i component Δvi: Molar volume of atom or atomic group of i component For example, a crystalline polyester composed of nonanediol and sebacic acid is represented by a repeating unit It is composed of atomic groups (—COO) × 2 + (— CH ₂ ) × 17, and the calculated SP value is obtained by the following equation.
δi = [Δei / Δvi] ^1/2 = [{(4300) × 2 + (1180) × 17} / {(18) × 2 + (16.1) × 17}] ^1/2
The SP value (δi) is 9.63.
In the present invention, the ratio of the crystalline resin to the amorphous resin on a mass basis is preferably from 5:95 to 50:50, more preferably from 10:90 to 40:60, and more preferably from 15:90 to 40:60. : 85 to 30:70.

<Colorant>
Examples of the coloring agent include known organic pigments or dyes, carbon black, and magnetic powder.
Examples of the cyan coloring agent include a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound. Specifically, C.I. I. Pigment Blue 1, C.I. I. Pigment Blue 7, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 62, C.I. I. Pigment Blue 66.
Examples of the magenta coloring agent include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Violet 19, C.I. I. Pigment Red 23, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 48: 4, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 81: 1, C.I. I. Pigment Red 122, C.I. I. Pigment red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 166, C.I. I. Pigment Red 169, C.I. I. Pigment Red 177, C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 202, C.I. I. Pigment Red 206, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 254.
Examples of the yellow colorant include a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound, and an allylamide compound. Specifically, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment Yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment Yellow 151, C. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 181, C.I. I. Pigment Yellow 191, C.I. I. Pigment Yellow 194.
Examples of the black colorant include carbon black, magnetic powder, and a black color tone using a yellow colorant, a magenta colorant, and a cyan colorant.
These colorants can be used alone or as a mixture, or in the form of a solid solution.
The colorant may be selected from the viewpoints of hue angle, saturation, brightness, light fastness, OHP transparency, and dispersibility in toner.
The content of the colorant is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component constituting the toner.

<Release agent>
Examples of the release agent include low molecular weight polyolefins such as polyethylene; silicones having a melting point (softening point) upon heating; fatty acid amides such as oleamide, erucamide, ricinoleamide, and stearamide. Ester waxes such as stearyl stearate; vegetable waxes such as carnauba wax, rice wax, candelilla wax, wood wax and jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin. Mineral and petroleum waxes such as waxes, microcrystalline waxes, Fischer-Tropsch waxes, and ester waxes; and modified products thereof.
The content of the release agent is preferably 1 to 25 parts by mass with respect to 100 parts by mass of the resin component constituting the toner.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but embodiments of the present invention are not limited thereto. Unless otherwise specified, all parts and percentages in Examples and Comparative Examples are based on mass.

<Production of amorphous resin fine particles 1>
200 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries)
120 g of polyester resin A
[Composition (molar ratio) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: isophthalic acid: terephthalic acid = 100: 50: 50], number average molecular weight (Mn) = 4 , 600, weight average molecular weight (Mw) = 16,500, peak molecular weight (Mp) = 10,400, Mw / Mn = 3.6, softening temperature (Tm) = 122 ° C, glass transition temperature (Tg) = 70 ° C. , Acid value = 13 mgKOH / g]
0.6 g of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK)
After mixing the above, the mixture was stirred for 12 hours to dissolve the resin.
Next, 2.7 g of N, N-dimethylaminoethanol was added, and an ultrahigh-speed stirrer T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primix).
Further, 360 g of ion-exchanged water was added at a rate of 1 g / min to precipitate resin fine particles. Thereafter, the tetrahydrofuran was removed using an evaporator to obtain amorphous resin fine particles 1 and a dispersion thereof.
The 50% particle size (d50) based on the volume distribution of the amorphous resin fine particles 1 was measured using a dynamic light scattering type particle size distribution meter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.13 μm.

<Production of amorphous resin fine particles 2>
Polyester resin A was converted to polyester resin B [composition (molar ratio) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.0) -2,2- Bis (4-hydroxyphenyl) propane: terephthalic acid = 35: 15: 50], Mn = 4,500, Mw = 12,300, Mw / Mn = 2.9, Tm = 11
Amorphous resin fine particles 2 and a dispersion thereof were obtained in the same manner as in the production of amorphous resin fine particles 1 except that the temperature was changed to 5 ° C., Tg = 65 ° C., and the acid value = 12 mg KOH / g]. The 50% particle size (d50) based on the volume distribution of the obtained amorphous resin fine particles 2 was 0.12 μm.

<Production of amorphous resin fine particles 3>
Polyester resin A was converted to polyester resin C [composition (molar ratio) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.0) -2,2- Bis (4-hydroxyphenyl) propane: terephthalic acid = 25: 25: 50], Mn = 3,500, Mw = 10,300, Mw / Mn = 2.9, Tm = 110 ° C., Tg = 60 ° C., acid Amorphous resin fine particles 3 and a dispersion thereof were obtained in the same manner as in the production of amorphous resin fine particles 1 except that the value was changed to 12 mgKOH / g]. The 50% particle size (d50) based on the volume distribution of the obtained amorphous resin fine particles 3 was 0.12 μm.

<Production of amorphous resin fine particles 4>
Polyester resin A was converted to polyester resin D [composition (molar ratio) [polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane: terephthalic acid = 50: 50], Mn = 3,900 , Mw = 12,300, Mw / Mn = 3.1, Tm = 109 ° C., Tg = 58 ° C., acid value = 12 mgKOH / g] in the same manner as in the production of the amorphous resin fine particles 1, Amorphous resin fine particles 4 and a dispersion thereof were obtained. The 50% particle size (d50) based on the volume distribution of the obtained amorphous resin fine particles 4 was 0.12 μm.

<Production of amorphous resin fine particles 5>
200 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries)
Styrene acrylic resin A 120g
[Composition (molar ratio) [styrene: butyl acrylate: stearyl acrylate: acrylic acid = 75: 10: 10: 5], number average molecular weight (Mn) = 15,600, weight average molecular weight (Mw) = 36,500 , Peak molecular weight (Mp) = 30,400, Mw / Mn = 2.3, softening temperature (Tm) = 122 ° C., glass transition temperature (Tg) = 57 ° C.]
0.6 g of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK)
After mixing the above, the mixture was stirred for 12 hours to dissolve the resin.
Next, 4.0 g of N, N-dimethylaminoethanol was added, and an ultrahigh-speed stirring device T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primix).
Further, 360 g of ion-exchanged water was added at a rate of 1 g / min to precipitate resin fine particles. Then, after dispersing for about 1 hour using a high pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo), tetrahydrofuran was removed using an evaporator to obtain amorphous resin fine particles 5 and a dispersion thereof.
The 50% particle size (d50) based on the volume distribution of the amorphous resin fine particles 5 was measured using a dynamic light scattering type particle size distribution meter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.

<Production of crystalline resin fine particles 1>
200 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries)
120 g of crystalline polyester A
[Composition (molar ratio) [1,9-nonanediol: sebacic acid = 100: 100], number average molecular weight (Mn) = 5,500, weight average molecular weight (Mw) = 15,500, peak molecular weight (Mp) = 11,400, Mw / Mn = 2.8, melting point = 72 ° C., acid value = 13 mgKOH / g] anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 0.6 g
After mixing the above, the mixture was heated to 50 ° C. and stirred for 3 hours to dissolve the resin.
Next, 2.7 g of N, N-dimethylaminoethanol was added, and an ultrahigh-speed stirrer T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primix).
Further, 360 g of ion-exchanged water was added at a rate of 1 g / min to precipitate resin fine particles. Thereafter, tetrahydrofuran was removed using an evaporator to obtain crystalline resin fine particles 1 and a dispersion thereof.
The 50% particle size (d50) based on the volume distribution of the crystalline resin fine particles 1 was measured using a dynamic light scattering type particle size distribution meter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.30 μm.

<Production of crystalline resin fine particles 2>
The crystalline polyester A was converted into the crystalline polyester B [composition (molar ratio) [1,6-hexanediol: sebacic acid = 100: 100], Mn = 4,400, Mw = 11,300, Mw / Mn = 2. 5, crystalline resin fine particles 2 and a dispersion thereof were obtained in the same manner as in the production of crystalline resin fine particles 1 except that the melting point was changed to 68 ° C. and the acid value was changed to 12 mg KOH / g. The 50% particle size (d50) based on the volume distribution of the obtained crystalline resin fine particles 2 was 0.20 μm.

<Production of crystalline resin fine particles 3>
Crystalline polyester A was converted to crystalline polyester C [composition (molar ratio) [1,12-dodecanediol: sebacic acid = 100: 100], Mn = 3,500, Mw = 10,300, Mw / Mn = 2. 9, melting point = 87 ° C., acid value = 12 mg KOH / g], and crystalline resin fine particles 3 and a dispersion thereof were obtained in the same manner as in the production of crystalline resin fine particles 1. The 50% particle size (d50) based on the volume distribution of the obtained crystalline resin fine particles 3 was 0.32 μm.

<Production of crystalline resin fine particles 4>
200 g of toluene (manufactured by Wako Pure Chemical Industries)
Crystalline acrylic resin A 120g
[Composition (molar ratio) [behenyl acrylate: 100], number average molecular weight (Mn) = 10,500, weight average molecular weight (Mw) = 32,500, peak molecular weight (Mp) = 27,400, Mw / Mn = 3 .2, melting point = 60 ° C.]
Anionic surfactant (Neogen RK manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 6g
After mixing the above, the mixture was heated to 50 ° C. and stirred for 3 hours to dissolve the resin.
Then, an ultra-high-speed stirring device T. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primix).
Further, 360 g of ion-exchanged water was added at a rate of 10 g / min to precipitate resin fine particles. Then, after dispersing for about 1 hour using a high pressure impact dispersing machine Nanomizer (manufactured by Yoshida Kikai Kogyo), toluene was removed using an evaporator to obtain crystalline resin fine particles 4 and a dispersion thereof.
The 50% particle size (d50) based on the volume distribution of the crystalline resin fine particles 4 was measured using a dynamic light scattering type particle size distribution meter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.32 μm.

<Solubility test of amorphous resin and crystalline resin>
To 1 L of each of the various organic solvents shown in Table 1, the above-mentioned polyester resins A to D, styrene acrylic resin A, crystalline polyesters A to C, and crystalline acrylic resin A were added in a predetermined mass, and the solvent treatment described below was performed. After stirring for 12 hours in an environment of 25 ° C., which is the processing temperature of the process, the solubility was evaluated. Table 1 shows the evaluation results.
From the solubility test of each resin, as the organic solvent to be added in the solvent treatment step during the production of the toner described below, ethyl acetate which is a good solvent for the amorphous resin and a poor solvent for the crystalline resin , Methyl ethyl ketone (MEK), acetone, and methyl acetate.
(Evaluation criteria)
A: completely dissolved when 100 g of resin was added, and a transparent liquid was obtained. B: completely dissolved when 10 g of resin was added, and a transparent liquid was obtained. Insoluble substances were observed in 100 g of resin. A non-uniform liquid is obtained. C: When 10 g of resin is added, insolubles are observed and a non-uniform liquid is obtained.

<Production of colorant fine particles>
-Coloring agent 10.0 parts by mass (Cyan pigment manufactured by Dainichi Seika: Pigment Blue 15: 3)
・ 1.5 parts by mass of anionic surfactant (manufactured by Daiichi Kogyo Seiyaku; Neogen RK) ・ 88.5 parts by mass of ion-exchange water For about 1 hour to prepare a dispersion of colorant fine particles in which the colorant is dispersed.
The 50% particle size (d50) based on the volume distribution of the obtained colorant fine particles was measured using a dynamic light scattering type particle size distribution analyzer (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.

<Manufacture of release agent fine particles>
Release agent (HNP-51, melting point: 78 ° C., manufactured by Nippon Seiwa) 20.0 parts by mass 0 parts by mass After charging the mixture into a mixing vessel equipped with a stirrer, the mixture was heated to 90 ° C. and circulated through a CLEARMIX W motion (manufactured by M Technique) while shearing with a rotor outer diameter of 3 cm and a clearance of 0.3 mm. At the site, the mixture was stirred under the conditions of a rotor rotation number of 19000 rpm and a screen rotation number of 19000 rpm, and subjected to a dispersion treatment for 60 minutes.
Thereafter, the dispersion was cooled to 40 ° C. under the cooling conditions of a rotor rotation speed of 1000 rpm, a screen rotation speed of 0 rpm, and a cooling rate of 10 ° C./min, to obtain a dispersion of release agent fine particles. The 50% particle size (d50) based on the volume distribution of the release agent fine particles was measured using a dynamic light scattering type particle size distribution meter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.

<Example 1>
(Granulation process_aggregation process)
-320 parts by mass of the dispersion of the amorphous resin fine particles 1-80 parts by mass of the dispersion of the crystalline resin fine particles 1-50 parts by mass of the dispersion of the colorant fine particles-50 parts by mass of the dispersion of the release agent fine particles-ion exchange water 400 parts by mass Each of the above materials was put into a round stainless steel flask, mixed, and then added to 98 parts by mass of ion-exchanged water with an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved. (Ultra Turrax T50) at 5000 rpm for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. Hold at 58 ° C for 1 hour, and the volume average particle size is about 6
. 0 μm aggregated particles were obtained.
(Compatibilization process)
An aqueous solution obtained by dissolving 20 parts by mass of trisodium citrate in 380 parts by mass of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85 ° C.
After keeping at 85 ° C. for 2 hours, the obtained particles had a volume average particle diameter of about 5.8 μm and an average circularity of 0.968, and sufficiently fused toner particles were obtained.
The average degree of circularity was calculated by using a flow-type particle image measuring device “FPIA-3000” (manufactured by Sysmex Corporation) in accordance with the operation manual of the device.
(Solvent treatment process)
The aqueous dispersion of the toner particles obtained in the compatibilization step was cooled to 25 ° C. while maintaining the stirring, 15 parts by mass of ethyl acetate was added, and the mixture was kept sealed for 3 hours.
Thereafter, the pressure is reduced using an evaporator while keeping the temperature at 25 ° C., and the ethyl acetate is removed. After filtration and solid-liquid separation, the residue is sufficiently washed with ion-exchanged water and dried using a vacuum dryer. As a result, toner particles 1 having a volume average particle size of 5.4 μm were obtained. Table 2 shows the formulation and characteristics of the toner particles 1.

<Example 2>
Toner particles 2 were obtained in the same manner as in Example 1, except that the dispersion of the amorphous resin fine particles 1 was changed to the dispersion of the amorphous resin fine particles 2. The volume average particle size of the obtained toner particles 2 was 5.5 μm. Table 2 shows the formulation and properties of the toner particles 2.

<Example 3>
Except that the dispersion liquid of the amorphous resin fine particles 1 was changed to the dispersion liquid of the amorphous resin fine particles 3, and the treatment temperature in the aggregation step was changed from 58 ° C to 53 ° C, Thus, toner particles 3 were obtained. The volume average particle diameter of the obtained toner particles 3 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 3.

<Example 4>
Toner particles 4 were obtained in the same manner as in Example 1, except that the heating temperature in the compatibilizing step was changed from 85 ° C to 80 ° C. The volume average particle diameter of the obtained toner particles 4 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 4.

<Example 5>
Toner particles 5 were obtained in the same manner as in Example 1, except that the heating temperature in the compatibilizing step was changed from 85 ° C to 95 ° C. The volume average particle diameter of the obtained toner particles 5 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 5.

<Example 6>
Toner particles 6 were obtained in the same manner as in Example 1, except that 15 parts by mass of ethyl acetate added in the solvent treatment step was changed to 3 parts by mass of ethyl acetate. The volume average particle size of the obtained toner particles 6 was 5.9 μm. Table 2 shows the formulation and properties of the toner particles 6.

<Example 7>
Toner particles 7 were obtained in the same manner as in Example 1, except that 15 parts by mass of ethyl acetate added in the solvent treatment step was changed to 60 parts by mass of ethyl acetate. The volume average particle size of the obtained toner particles 7 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 7.

<Example 8>
(Granulation process_aggregation process)
-320 parts by mass of the dispersion of the amorphous resin fine particles 1-80 parts by mass of the dispersion of the crystalline resin fine particles 1-50 parts by mass of the dispersion of the colorant fine particles-50 parts by mass of the dispersion of the release agent fine particles-ion exchange water 400 parts by mass Each of the above materials was put into a round stainless steel flask, mixed, and then added to 98 parts by mass of ion-exchanged water with an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved. (Ultra Turrax T50) at 5000 rpm for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. The mixture was kept at 58 ° C. for 1 hour to obtain aggregated particles having a volume average particle size of about 6.0 μm.
(Compatibilization process)
An aqueous solution obtained by dissolving 20 parts by mass of trisodium citrate in 380 parts by mass of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85 ° C.
After keeping at 85 ° C. for 2 hours, the obtained particles had a volume average particle diameter of about 5.8 μm and an average circularity of 0.968, and sufficiently fused toner particles were obtained.
(Solvent treatment process)
The aqueous dispersion of toner particles obtained in the compatibilization step was cooled to 25 ° C. while cooling water was placed in a water bath, and stirring was continued, and 2800 parts by mass of ion-exchanged water was added. A portion of ethyl acetate was added and kept closed for 3 hours.
Thereafter, the pressure is reduced using an evaporator while maintaining the temperature at 25 ° C., and the ethyl acetate is removed. Thus, toner particles 8 having a volume average particle size of 5.4 μm were obtained. Table 2 shows the formulation and characteristics of the toner particles 8.

<Example 9>
Toner particles 9 were obtained in the same manner as in Example 1, except that the dispersion of the crystalline resin fine particles 1 was changed to the dispersion of the crystalline resin fine particles 2. The volume average particle diameter of the obtained toner particles 9 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 9.

<Example 10>
A toner was prepared in the same manner as in Example 1, except that the dispersion of the crystalline resin fine particles 1 was changed to the dispersion of the crystalline resin fine particles 3, and the heating temperature in the compatibilizing step was changed from 85 ° C. to 90 ° C. Particle 10 was obtained. The volume average particle diameter of the obtained toner particles 10 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 10.

<Example 11>
The dispersion of the amorphous resin fine particles 1 is changed to the dispersion of the amorphous resin fine particles 5, the dispersion of the crystalline resin fine particles 1 is changed to the dispersion of the crystalline resin fine particles 4, and the aggregation step is performed. Except that the temperature was changed from 58 ° C. to 53 ° C., toner particles 11 were obtained in the same manner as in Example 1. The volume average particle size of the obtained toner particles 11 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 11.

<Example 12>
Toner particles 12 were obtained in the same manner as in Example 1, except that 15 parts by mass of ethyl acetate added in the solvent treatment step was changed to 30 parts by mass of methyl ethyl ketone. The volume average particle diameter of the obtained toner particles 12 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 12.

<Example 13>
Toner particles 13 were obtained in the same manner as in Example 1, except that 15 parts by mass of ethyl acetate added in the solvent treatment step was changed to 50 parts by mass of acetone. The volume average particle diameter of the obtained toner particles 13 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 13.

<Example 14>
Toner particles 14 were obtained in the same manner as in Example 1, except that 15 parts by mass of ethyl acetate added in the solvent treatment step was changed to 30 parts by mass of methyl acetate. The volume average particle diameter of the obtained toner particles 14 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 14.

<Example 15>
(Compatibilization process)
200 g of toluene (manufactured by Wako Pure Chemical Industries)
96 g of polyester resin A
[Composition (molar ratio) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: isophthalic acid: terephthalic acid = 100: 50: 50], number average molecular weight (Mn) = 4 , 600, weight average molecular weight (Mw) = 16,500, peak molecular weight (Mp) = 10,400, Mw / Mn = 3.6, softening temperature (Tm) = 122 ° C, glass transition temperature (Tg) = 70 ° C. , Acid value = 13 mgKOH / g]
24 g of crystalline polyester A
[Composition (molar ratio) [1,9-nonanediol: sebacic acid = 100: 100], number average molecular weight (Mn) = 5,500, weight average molecular weight (Mw) = 15,500, peak molecular weight (Mp) = 11,400, Mw / Mn = 2.8, melting point = 78 ° C., acid value = 13 mgKOH / g] Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 g
After mixing the above, the mixture was heated to 80 ° C., stirred for 3 hours, and dissolved.
Then, an ultra-high-speed stirring device T. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primix).
Further, 360 g of ion-exchanged water was added at a rate of 10 g / min to precipitate resin fine particles. Then, after dispersing for about 1 hour using a high pressure impact type dispersing machine Nanomizer (manufactured by Yoshida Kikai Co., Ltd.), toluene is removed using an evaporator, and composite fine particles 1 of an amorphous resin and a crystalline resin and a dispersion thereof. I got
The 50% particle size (d50) based on the volume distribution of the composite fine particles 1 of the amorphous resin and the crystalline resin was measured using a dynamic light scattering type particle size distribution meter (Nanotrack: manufactured by Nikkiso Co., Ltd.). It was 19 μm.
(Solvent treatment process)
15 parts by mass of ethyl acetate was added to the aqueous dispersion of the composite fine particles 1 of the amorphous resin and the crystalline resin obtained in the compatibilization step under an environment of 25 ° C. while maintaining the stirring, followed by sealing for 3 hours. It was kept in a state.
Thereafter, the pressure was reduced using an evaporator while keeping the temperature at 25 ° C. to remove ethyl acetate. (Granulation process_aggregation process)
-400 parts by mass of the dispersion of the composite fine particles 1 of the amorphous resin and the crystalline resin-50 parts by mass of the dispersion of the colorant particles-50 parts by mass of the dispersion of the release agent particles-400 parts by mass of ion-exchanged water The materials were put into a round stainless steel flask and mixed, and then, an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved in 98 parts by mass of ion-exchanged water was added thereto, and a homogenizer (IKA: Ultra Turrax T50) was added. ) At 5000 rpm for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. The mixture was kept at 58 ° C. for 1 hour to obtain aggregated particles having a volume average particle size of about 6.0 μm.
After adding an aqueous solution obtained by dissolving 20 parts by mass of trisodium citrate to 380 parts by mass of ion-exchanged water to the dispersion containing the aggregated particles, 10 parts by mass of sodium chloride was added to 90 parts by mass of ion-exchanged water. An aqueous solution in which a part was dissolved was added and heated to 68 ° C.
After keeping at 68 ° C. for 12 hours, the obtained particles had a volume average particle diameter of about 5.8 μm and an average circularity of 0.945, and sufficiently fused toner particles were obtained.
The obtained aqueous dispersion of toner particles was cooled to 25 ° C. while cooling water was placed in a water bath, and the mixture was filtered and solid-liquid separated, and the residue was sufficiently ion-exchanged with ion-exchanged water. The toner particles 15 having a volume average particle size of 5.4 μm were obtained by washing with a vacuum dryer. Table 2 shows the formulation and characteristics of the toner particles 15.

<Example 16>
(Compatibilization process)
-80 parts by mass of polyester resin A-20 parts by mass of crystalline polyester A-5 parts by mass of colorant (Cyan pigment: Pigment Blue 15: 3 manufactured by Dainichi Seika)
-Release agent (HNP-51, melting point: 78 ° C, manufactured by Nippon Seiro) 5 parts by mass After pre-mixing the above raw materials with a Henschel mixer, a twin-screw kneading extruder (PCM-30: Ikegai) set to 130 ° C and 200 rpm Kneading process for 2 hours using an ironworks company).
(Granulation process_Pulverization process)
After cooling the obtained kneaded material and coarsely pulverizing it with a cutter mill, the obtained coarsely pulverized material is finely pulverized using a turbo mill T-250 (manufactured by Turbo Kogyo Co., Ltd.), and a multi-divided classifier utilizing the Coanda effect. To obtain toner particles having a volume average particle size of 5.8 μm.
(Solvent treatment process)
100 parts by mass of the toner particles having undergone the compatibilizing step and the granulating step are charged into a round stainless steel flask, and 10 parts by weight of an anionic surfactant (Neogen RK manufactured by Daiichi Kogyo Seiyaku) is added to 890 parts by weight of ion-exchanged water. An aqueous solution in which the mass part was dissolved was further added, and the mixture was irradiated with ultrasonic waves for 1 hour using an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.). Obtained.
Thereafter, the flask was placed in a water bath maintained at a temperature of 25 ° C., the aqueous dispersion of toner particles was adjusted to 25 ° C., and 15 parts by mass of ethyl acetate was added while stirring the aqueous dispersion with a stirring blade. And kept closed for 3 hours.
Thereafter, ethyl acetate was removed using an evaporator, and the mixture was filtered and solid-liquid separated. The residue was sufficiently washed with ion-exchanged water and dried using a vacuum drier to obtain a volume average particle size of 5%. 0.8 μm of toner particles 16 were obtained. Table 2 shows the formulation and characteristics of the toner particles 16.

<Example 17>
(Granulation process_Suspension polymerization process)
18.0 parts by mass of a cyan pigment (Pigment Blue 15: 3 manufactured by Dainichi Seika) as a coloring agent, 180 parts by mass of styrene as a polymerizable monomer, and 130 parts by mass of glass beads (1 mm in diameter) are mixed, and an attritor [ Nippon Coke Industry Co., Ltd.] and filtered through a mesh to obtain a colorant dispersion.
132 parts by mass of a colorant dispersion 46 parts by mass of styrene 17 parts by mass of n-butyl acrylate 17 parts by mass of n-stearyl acrylate 25 parts by mass of a mold release agent (HNP-51, melting point 78 ° C., manufactured by Nippon Seiro)・ 2 parts by mass of aluminum salicylate compound (Bontron E-88, manufactured by Orient Chemical Co., Ltd.)
・ 0.1 parts by mass of divinylbenzene ・ 10 parts by mass of polyester resin A ・ 10 parts by mass of crystalline acrylic resin A K. 710 parts by mass of ion-exchanged water and 450 parts by mass of 0.1 mol / L-Na ₃ PO ₄ aqueous solution were added to a 2-liter four-necked flask equipped with a homomixer [manufactured by Primix Co., Ltd.], and the rotation speed was adjusted to 12,000 rpm. And heated to 60 ° C.
68 parts by mass of a 1.0 mol / L-CaCl ₂ aqueous solution was gradually added thereto to prepare an aqueous medium containing a minute hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . Next, the above composition was heated to 60 ° C. K. Using a homomixer [manufactured by Primix Co., Ltd.], the mixture was uniformly dissolved and dispersed at 5000 rpm.
To this, 10 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added, and the mixture was charged into the above aqueous medium, and granulated for 15 minutes while maintaining the rotation speed at 12,000 rpm. Then, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, and polymerization was continued at a liquid temperature of 60 ° C. for 5 hours. Then, the liquid temperature was raised to 80 ° C. and polymerization was continued for 8 hours to obtain toner particles. Was.
(Compatibilization process)
After the completion of the polymerization reaction, the mixture was once cooled to 30 ° C. and kept in a sealed state at 90 ° C., which is higher than the melting point of the crystalline acrylic resin A, for 3 hours.
(Solvent treatment process)
The aqueous dispersion of the toner particles obtained in the compatibilizing step was cooled to 25 ° C. while maintaining the stirring, 40 parts by mass of ethyl acetate was added, and the mixture was kept sealed for 3 hours.
Thereafter, the pressure was reduced using an evaporator while maintaining the temperature at 25 ° C., and after removing ethyl acetate, dilute hydrochloric acid was added with stirring, and the mixture was stirred at pH 1.5 for 2 hours and contained Ca ₃ (PO ₄ ) ₂ . After dissolving the compound of phosphoric acid and calcium, the mixture was subjected to solid-liquid separation with a filter to obtain toner particles.
This was poured into water, stirred, and again made into a dispersion, and then subjected to solid-liquid separation with a filter. The re-dispersion of the toner particles in water and the solid-liquid separation were repeated until the phosphoric acid and calcium compounds containing Ca ₃ (PO ₄ ) ₂ were sufficiently removed.
Thereafter, the toner particles finally solid-liquid separated were sufficiently dried with a dryer to obtain toner particles 17 having a volume average particle diameter of 7.2 μm. Table 2 shows the formulation and characteristics of the toner particles 17.

<Comparative Example 1>
(Granulation process_aggregation process)
-320 parts by mass of the dispersion of the amorphous resin fine particles 1-80 parts by mass of the dispersion of the crystalline resin fine particles 1-50 parts by mass of the dispersion of the colorant fine particles-50 parts by mass of the dispersion of the release agent fine particles-ion exchange water 400 parts by mass Each of the above materials was put into a round stainless steel flask, mixed, and then added to 98 parts by mass of ion-exchanged water with an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved. (Ultra Turrax T50) at 5000 rpm for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. The mixture was kept at 58 ° C. for 1 hour to obtain aggregated particles having a volume average particle size of about 6.0 μm.
(Compatibilization process_Fusion process)
After adding an aqueous solution obtained by dissolving 20 parts by mass of trisodium citrate to 380 parts by mass of ion-exchanged water to the dispersion liquid containing the aggregated particles, the mixture was heated to 85 ° C. while continuing to stir. It was kept sealed for hours.
The obtained particles had a volume average particle size of about 5.8 μm and an average circularity of 0.968, and sufficiently fused toner particles were obtained.
Subsequently, water is poured into a water bath, the aqueous dispersion of the toner particles is cooled to 25 ° C., and filtered and solid-liquid separated. By drying, toner particles 18 having a volume average particle size of 5.4 μm were obtained. Table 2 shows the formulation and characteristics of the toner particles 18.

<Comparative Example 2>
Toner particles 19 were obtained in the same manner as in Comparative Example 1, except that the dispersion of the amorphous resin fine particles 1 was changed to the dispersion of the amorphous resin fine particles 4. The volume average particle diameter of the obtained toner particles 19 was 5.8 μm. Table 2 shows the formulation and characteristics of the toner particles 19.

<Comparative Example 3>
(Granulation process_aggregation process)
-320 parts by mass of the dispersion of the amorphous resin fine particles 4-80 parts by mass of the dispersion of the crystalline resin fine particles 1-50 parts by mass of the dispersion of the colorant fine particles-50 parts by mass of the dispersion of the release agent fine particles-ion exchange water 400 parts by mass Each of the above materials was put into a round stainless steel flask, mixed, and then added to 98 parts by mass of ion-exchanged water with an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved. (Ultra Turrax T50) at 5000 rpm for 10 minutes.
Thereafter, the mixture was heated to 50 ° C. in a heating water bath using a stirring blade while appropriately adjusting the rotation speed so that the mixture was stirred. The mixture was kept at 50 ° C. for 1 hour to obtain aggregated particles having a volume average particle size of about 6.0 μm.
(Compatibilization process)
An aqueous solution obtained by dissolving 20 parts by mass of trisodium citrate in 380 parts by mass of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85 ° C.
After keeping at 85 ° C. for 2 hours, the obtained particles had a volume average particle diameter of about 5.8 μm and an average circularity of 0.968, and sufficiently fused toner particles were obtained.
(Solvent treatment process)
The aqueous dispersion of toner particles obtained in the compatibilization step was cooled to 25 ° C. while cooling water was placed in a water bath, and stirring was continued, and 2800 parts by mass of ion-exchanged water was added. A portion of ethyl acetate was added and kept closed for 3 hours.
Thereafter, the pressure is reduced using an evaporator while maintaining the temperature at 25 ° C., and the ethyl acetate is removed. As a result, toner particles 20 having a volume average particle size of 5.4 μm were obtained. Table 2 shows the formulation and characteristics of the toner particles 20.

<Comparative Example 4>
(Granulation process_aggregation process)
-320 parts by mass of the dispersion of the amorphous resin fine particles 1-80 parts by mass of the dispersion of the crystalline resin fine particles 1-50 parts by mass of the dispersion of the colorant fine particles-50 parts by mass of the dispersion of the release agent fine particles-ion exchange water 400 parts by mass Each of the above materials was put into a round stainless steel flask, mixed, and then added to 98 parts by mass of ion-exchanged water with an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved. (Ultra Turrax T50) at 5000 rpm for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. The mixture was kept at 58 ° C. for 1 hour to obtain aggregated particles having a volume average particle size of about 6.0 μm.
(Compatibilization process_Fusion process)
After adding an aqueous solution obtained by dissolving 20 parts by mass of trisodium citrate to 380 parts by mass of ion-exchanged water to the dispersion containing the aggregated particles, the mixture was heated to 85 ° C. while continuing to stir, It was kept sealed for hours.
The obtained particles had a volume average particle size of about 5.8 μm and an average circularity of 0.968, and a sufficiently fused toner was obtained.
(Annealing process by heat treatment)
Subsequently, water was poured into a water bath, and the aqueous dispersion of toner particles was cooled to 25 ° C., and as an annealing treatment by heating, heated again to 50 ° C. and held for 12 hours. Thereafter, the aqueous dispersion of the toner particles is cooled to 25 ° C., filtered, and solid-liquid separated. Was 5.4 μm. Table 2 shows the formulation and characteristics of the toner particles 21.

<Comparative Example 5>
(Granulation process_aggregation process)
-320 parts by mass of the dispersion of the amorphous resin fine particles 1-80 parts by mass of the dispersion of the crystalline resin fine particles 1-50 parts by mass of the dispersion of the colorant fine particles-50 parts by mass of the dispersion of the release agent fine particles-ion exchange water 400 parts by mass Each of the above materials was put into a round stainless steel flask, mixed, and then added to 98 parts by mass of ion-exchanged water with an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved. (Ultra Turrax T50) at 5000 rpm for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. The mixture was kept at 58 ° C. for 1 hour to obtain aggregated particles having a volume average particle size of about 6.0 μm.
(Compatibilization process_Fusion process)
After adding an aqueous solution obtained by dissolving 20 parts by mass of trisodium citrate to 380 parts by mass of ion-exchanged water to the dispersion containing the aggregated particles, the mixture was heated to 85 ° C. while continuing to stir, It was kept sealed for hours.
The obtained particles had a volume average particle size of about 5.8 μm and an average circularity of 0.968, and a sufficiently fused toner was obtained.
(Solvent treatment process)
The aqueous dispersion of toner particles obtained in the compatibilization step was cooled to 25 ° C. while cooling water was placed in a water bath, and stirring was continued, and 2800 parts by mass of ion-exchanged water was added. Toluene was added thereto and kept in a sealed state for 3 hours. As a result, coarse particles in which toner particles were fused together were observed.
Thereafter, the pressure was reduced using an evaporator while maintaining the temperature at 25 ° C., the toluene was removed, and filtration and solid-liquid separation were performed. No toner particles having a particle size that can be evaluated as described below were obtained (toner particles 22).

<Comparative Example 6>
(Granulation process_aggregation process)
-320 parts by mass of the dispersion of the amorphous resin fine particles 1-80 parts by mass of the dispersion of the crystalline resin fine particles 1-50 parts by mass of the dispersion of the colorant fine particles-50 parts by mass of the dispersion of the release agent fine particles-ion exchange water 400 parts by mass Each of the above materials was put into a round stainless steel flask, mixed, and then added to 98 parts by mass of ion-exchanged water with an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved. (Ultra Turrax T50) at 5000 rpm for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. The mixture was kept at 58 ° C. for 1 hour to obtain aggregated particles having a volume average particle size of about 6.0 μm.
(Compatibilization process_Fusion process)
After adding an aqueous solution obtained by dissolving 20 parts by mass of trisodium citrate to 380 parts by mass of ion-exchanged water to the dispersion containing the aggregated particles, the mixture was heated to 85 ° C. while continuing to stir, It was kept sealed for hours.
The obtained particles had a volume average particle size of about 5.8 μm and an average circularity of 0.968, and a sufficiently fused toner was obtained.
(Solvent treatment process)
The aqueous dispersion of the toner particles obtained in the compatibilizing step was cooled to 25 ° C. while cooling water was placed in a water bath, and stirring was continued, and 2800 parts by mass of ion-exchanged water was added. Of ethanol was added and kept closed for 3 hours.
Then, the pressure is reduced using an evaporator while keeping the temperature at 25 ° C., the ethanol is removed, and the mixture is filtered and solid-liquid separated. The filtrate is sufficiently washed with ion-exchanged water, and dried using a vacuum dryer. As a result, toner particles 23 having a volume average particle size of 5.4 μm were obtained. Table 2 shows the formulation and characteristics of the toner particles 23.

<Comparative Example 7>
(Granulation process_aggregation process)
-320 parts by mass of the dispersion of the amorphous resin fine particles 1-80 parts by mass of the dispersion of the crystalline resin fine particles 1-50 parts by mass of the dispersion of the colorant fine particles-50 parts by mass of the dispersion of the release agent fine particles-ion exchange water 400 parts by mass, 60 parts by mass of ethyl acetate The above-mentioned materials were put into a round stainless steel flask and mixed, and then an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved in 98 parts by mass of ion-exchanged water was added. Then, the mixture was dispersed at 5000 rpm for 10 minutes using a homogenizer (Ultra Turrax T50 manufactured by IKA).
Thereafter, the mixture was heated to 58 ° C. by using a stirring blade in a heating water bath while appropriately controlling the number of revolutions so as to stir the mixed solution. As a result, coarse particles in which the toners were fused were observed. The mixture was kept at 58 ° C. for 1 hour to obtain aggregated particles having a volume average particle size of about 12.0 μm.
(Compatibilization process_Fusion process)
After adding an aqueous solution obtained by dissolving 20 parts by mass of trisodium citrate to 380 parts by mass of ion-exchanged water to the dispersion containing the aggregated particles, the mixture was heated to 85 ° C. while continuing to stir, It was kept sealed for hours.
The obtained particles had a volume average particle size of about 13.8 μm and an average circularity of 0.968, and sufficiently fused toner particles were obtained.
Subsequently, water is poured into a water bath, the aqueous dispersion of the toner particles is cooled to 25 ° C., and after filtration and solid-liquid separation, the residue is sufficiently washed with ion-exchanged water, and is then dried using a vacuum dryer. Although dried, toner particles having a particle size that can be evaluated as described below were not obtained (toner particles 24).

<Comparative Example 8>
(Granulation process_aggregation process)
-320 parts by mass of the dispersion of the amorphous resin fine particles 1-80 parts by mass of the dispersion of the crystalline resin fine particles 1-50 parts by mass of the dispersion of the colorant fine particles-50 parts by mass of the dispersion of the release agent fine particles-ion exchange water 400 parts by mass Each of the above materials was put into a round stainless steel flask, mixed, and then added to 98 parts by mass of ion-exchanged water with an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved. (Ultra Turrax T50) at 5000 rpm for 10 minutes.
Thereafter, the mixture was heated to 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. The mixture was kept at 58 ° C. for 1 hour to obtain aggregated particles having a volume average particle size of about 5.8 μm.
(Compatibilization process_Fusion process)
After adding an aqueous solution obtained by dissolving 20 parts by mass of trisodium citrate to 380 parts by mass of ion-exchanged water, adding 60 parts by mass of ethyl acetate to the dispersion containing the aggregated particles while stirring is continued. Then, it was heated to 85 ° C. and kept in a sealed state for 2 hours.
The obtained particles had a volume average particle size of about 5.8 μm and an average circularity of 0.968, and sufficiently fused toner particles were obtained.
Subsequently, the pressure was reduced using an evaporator in a heated state to remove ethyl acetate. Then, cooling water was put into a water bath, and the mixture was cooled to 25 ° C. while stirring was continued. After filtration and solid-liquid separation of the obtained toner aqueous dispersion, the residue is sufficiently washed with ion-exchanged water and dried using a vacuum dryer, so that the toner particles having a volume average particle diameter of 5.4 μm are obtained. 25 was obtained. Table 2 shows the formulation and characteristics of the toner particles 25.

<Evaluation of toner characteristics>
Using the toner particles 1 to 25, the following evaluation was performed as the characteristic evaluation of the toner. The results are shown in Table 2.

<Evaluation of shelf life>
To 100 parts by mass of toner particles, 1.8 parts by mass of silica fine particles having a specific surface area of 200 m ² / g measured by the BET method and subjected to hydrophobic treatment with silicone oil were dry-mixed with a Henschel mixer (Mitsui Mining). Thus, a toner to which an external additive was added was prepared.
The toner was allowed to stand for 3 days in a thermo-hygrostat, and when sieved with a sieve having an opening of 75 μm for 300 seconds with a shaking width of 1 mm, the amount of toner remaining on the sieve was determined according to the following criteria. Was evaluated. Table 2 shows the evaluation results.
(Evaluation criteria)
A: Less than 10% of the amount of toner remaining on the sieve when sieved after standing in a thermo-hygrostat at a temperature of 55 ° C. and a humidity of 10% RH for 3 days B: A temperature of 55 ° C. and a humidity of 10% RH After sieving after standing for 3 days in a thermo-hygrostat, the amount of toner remaining on the sieve is 10% or more, but after standing for 3 days in a thermo-hygrostat at a temperature of 50 ° C. and a humidity of 10% RH The amount of toner remaining on the sieve after sieving was less than 10%. C: After being allowed to stand for 3 days in a thermo-hygrostat at a temperature of 50 ° C. and a humidity of 10% RH, the toner remained on the sieve when sieving. 10% or more toner

<Evaluation of low-temperature fixability>
To 100 parts by mass of toner particles, 1.8 parts by mass of a silica fine powder having a specific surface area of 200 m ² / g measured by the BET method and subjected to hydrophobic treatment with silicone oil was dry-mixed with a Henschel mixer (Mitsui Mining). Thus, a toner to which an external additive was added was prepared.
The two-component developer was prepared by mixing the toner and a ferrite carrier (average particle size: 42 μm) surface-coated with a silicone resin so that the toner concentration became 8% by mass.
The two-component developer was charged into a commercially available full-color digital copying machine (CLC1100, manufactured by Canon Inc.), and an unfixed toner image (0.6 mg / cm ² ) was formed on an image receiving paper (64 g / m ² ).
A fixing unit removed from a commercially available full-color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon Inc.) was modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed image was performed using this. At normal temperature and normal humidity, the process speed was set to 246 mm / sec, and the state when the unfixed image was fixed was visually evaluated. Table 2 shows the evaluation results.
(Evaluation criteria)
A: Fixable in a temperature range of 120 ° C. or less B: Fixable in a temperature range of higher than 120 ° C. and 125 ° C. or less C: Fixable in a temperature range of 125 ° C. or higher and 130 ° C. or less D: 130 ° C. E: Fixable in a temperature range below 140 ° C. E: There is a fixable region only in a temperature range higher than 140 ° C.

<Evaluation of chargeability>
To 100 parts by mass of toner particles, 1.8 parts by mass of a silica fine powder having a specific surface area of 200 m ² / g measured by the BET method and subjected to hydrophobic treatment with silicone oil was dry-mixed with a Henschel mixer (Mitsui Mining). Thus, a toner to which an external additive was added was prepared.
The two-component developer was prepared by mixing the toner and a ferrite carrier (average particle size: 42 μm) surface-coated with a silicone resin so that the toner concentration became 8% by mass.
Here, the charge amount of the toner was measured by an Espart analyzer manufactured by Hosokawa Micron Corporation. The Espart analyzer is a device that introduces sample particles into a detection unit (measurement unit) in which an electric field and an acoustic field are simultaneously formed, measures the moving speed of the particles by a laser Doppler method, and measures the particle size and the charge amount. .
The sample particles entering the measuring section of the apparatus fall while being deflected in the horizontal direction under the influence of the acoustic field and the electric field, and the beat frequency of this horizontal velocity is counted. The count value is input to the computer by interruption, and the particle size distribution or the charge amount distribution per unit particle size is displayed on the computer screen in real time. When a predetermined number of charge amounts are measured, the screen stops, and thereafter, the three-dimensional distribution of charge amount and particle size, the charge amount distribution by particle size, the average charge amount (coulomb / weight), and the like are displayed. Will be displayed.
The charge amount of the toner was measured by introducing the above-described two-component developer as sample particles into a measurement unit of an Espart analyzer.
After measuring the triboelectric charge of the initial toner by the above method, the two-component developer was allowed to stand in a constant temperature and humidity chamber (temperature: 30 ° C., humidity: 80% RH) for one week, and the triboelectric charge was measured again.
The measurement results were substituted into the following formula to calculate the retention of the triboelectric charge, and evaluated according to the following criteria. Table 2 shows the evaluation results.
Formula: Friction charge retention of toner (%) = [Amount of frictional charge of toner after one week] / [Amount of frictional charge of initial toner] × 100
(Evaluation criteria)
A: The toner has a frictional charge retention of 80% or more B: The toner has a frictional charge retention of less than 80% and 60% or more C: The toner has a frictional charge retention of less than 60%

Claims (11)

A method for producing a toner containing a crystalline resin and an amorphous resin compatible with the crystalline resin,
A compatibilizing step of compatibilizing the crystalline resin and the amorphous resin to obtain a compatibilized product, and
Including a solvent treatment step of treating the compatibilized product with an organic solvent,
Organic solvent is a good solvent of the non-crystalline resin, and, Ri poor solvent der of the crystalline resin,
The solvent treatment step, in an aqueous medium, method for producing a toner, wherein the step der Rukoto for processing compatibilizing material in the organic solvent. The compatibilizing step comprises:
Heating the crystalline resin and the amorphous resin above the melting point of the crystalline resin to obtain a compatibilized product by dissolving the crystalline resin and the amorphous resin, or
An organic solvent capable of dissolving the crystalline resin and the amorphous resin, dissolving the crystalline resin and the amorphous resin, compatibilizing the crystalline resin and the amorphous resin to form a compatibilized product. The method for producing a toner according to claim 1, which is a step of obtaining. The method for producing a toner according to claim 1, wherein the compatibilized product obtained by compatibilizing the crystalline resin and the amorphous resin in the compatibilizing step satisfies Formula 1 below. 4.
0.00 ≦ {Wt / (Wr × Z / 100)} ≦ 0.50 (Equation 1)
Wt: heat of fusion (J / g) derived from the crystalline resin at the time of the second temperature rise in the measurement of the compatibilized material using a differential scanning calorimeter (DSC)
Wr: heat of fusion (J / g) at the time of the second temperature rise in the measurement of the crystalline resin using a differential scanning calorimeter (DSC)
Z: Content ratio (% by mass) of the crystalline resin in the compatibilized product A good solvent for the amorphous resin is one in which the solubility of the amorphous resin at the processing temperature in the solvent treatment step is 100 g / L or more,
The poor solvent for the crystalline resin has a solubility of less than 10 g / L at the processing temperature in the solvent treatment step.
A method for producing the toner according to claim 1. The method for producing a toner according to claim 1, wherein the solvent-treated product obtained in the solvent treatment step satisfies the following expression (2).
1.00> {(Wta−Wt0) / (Wr0 × Z / 100)}> 0 (Equation 2)
Wta: heat of fusion (J / g) derived from the crystalline resin at the first temperature rise in the measurement of the solvent-treated product using a differential scanning calorimeter (DSC)
Wt0: heat of fusion (J / g) derived from the crystalline resin at the first temperature rise in the measurement of the compatibilized product using a differential scanning calorimeter (DSC)
Wr0: heat of fusion (J / g) at the first temperature rise in the measurement of the crystalline resin using a differential scanning calorimeter (DSC)
Z: Content ratio (% by mass) of the crystalline resin in the compatibilized product   The method for producing a toner according to claim 1, wherein a melting point of the crystalline resin is 50 ° C. or more and 100 ° C. or less.   The method for producing a toner according to any one of claims 1 to 6, wherein the crystalline resin is a crystalline polyester resin.   The method for producing a toner according to claim 1, wherein the organic solvent in the solvent treatment step is a hydrophilic solvent. Before the compatibilizing step, further including a granulating step,
The said granulation process is a process which contains the said crystalline resin and the said amorphous resin, and is a process of obtaining the particle whose volume average particle diameter is 3 micrometers or more and 10 micrometers or less, The Claims any one of Claims 1-8 . Manufacturing method of toner. Between the compatibilizing step and the solvent treatment step, further includes a granulation step,
Granulation process, contains a compatibilized material obtained by the compatibilizing step is a step of volume average particle diameter to obtain a 10μm particles below or 3 [mu] m, according to any one of claims 1-8 Production method of toner. After the solvent treatment step, further includes a granulation step,
Granulation step, contain a solvent-treated product obtained in the solvent treatment step is a step of volume average particle diameter to obtain a 10μm particles below or 3 [mu] m, according to any one of claims 1-8 Production method of toner.